Low-color scratch-resistant articles with a multilayer optical film

ABSTRACT

Embodiments of this disclosure pertain to articles that exhibit scratch-resistance and improved optical properties. In some examples, the article exhibits a color shift of about 2 or less, when viewed at an incident illumination angle in the range from about 0 degrees to about 60 degrees from normal under an illuminant. In one or more embodiments, the articles include a substrate, and an optical film disposed on the substrate. The optical film includes a scratch-resistant layer and an optical interference layer. The optical interference layer may include one or more sub-layers that exhibit different refractive indices. In one example, the optical interference layer includes a first low refractive index sub-layer and a second a second high refractive index sub-layer. In some instances, the optical interference layer may include a third sub-layer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application and claims the benefit of priority under 35 U.S.C. § 120 of Ser. No. 17/529,352, filed Nov. 18, 2021, still pending, which is a continuation application and claims the benefit of priority under 35 U.S.C. § 120 of Ser. No. 16/386,759, filed Apr. 17, 2019, now U.S. Pat. No. 11,231,526, which is a continuation application and claims the benefit of priority under 35 U.S.C. § 120 of Ser. No. 15/142,508, filed Apr. 29, 2016, now U.S. Pat. No. 10,444,408, which is a divisional application and claims the benefit of priority under 35 U.S.C. § 120 of Ser. No. 14/480,898, filed Sep. 9, 2014, now U.S. Pat. No. 9,366,784, which in turn claims the benefit of priority under 35 U.S.C. § 119 of U.S. Provisional Application Ser. No. 62/034,412 filed on Aug. 7, 2014, of U.S. Provisional Application Ser. No. 61/954,697 filed on Mar. 18, 2014, and of U.S. Provisional Application Ser. No. 61/877,568 filed on Sep. 13, 2013, the contents of which are relied upon and incorporated herein by reference in their entirety. Application Ser. No. 15/142,508 filed on Apr. 29, 2016 is a continuation-in-part application and claims the benefit of priority under 35 U.S.C. § 120 of U.S. Application Ser. No. 14/331,656 filed Jul. 15, 2014, now U.S. Pat. No. 9,079,802, which is a continuation and claims the benefit of priority under 35 U.S.C. § 120 of U.S. Application Ser. No. 14/262,066 filed on Apr. 25, 2014, now U.S. Pat. No. 9,359,261, which in turns claims the benefit of priority under 35 U.S.C. § 119 of U.S. Provisional Application Ser. No. 61/954,697 filed on Mar. 18, 2014, of U.S. Provisional Application Ser. No. 61/877,568 filed on Sep. 13, 2013, and of U.S. Provisional Application Ser. No. 61/820,407 filed on May 7, 2013, the contents of which are relied upon and incorporated herein by reference in their entirety.

BACKGROUND

The disclosure relates to articles with scratch resistance, abrasion resistance or a combination thereof, which also exhibit retained optical properties and more particularly to articles that exhibit a high hardness and low color shift when viewed at different incident illumination angles.

Cover and housing substrates are often used in consumer electronic products to protect critical devices within the product, to provide a user interface for input and/or display, and/or many other functions. Such consumer electronic products include mobile devices, such as smart phones, mp3 players and computer tablets. Cover and housing substrates may also be used in architectural articles, transportation-related articles, appliance articles, or any article that requires some transparency, scratch-resistance, abrasion resistance or a combination thereof. These applications and others also often demand durable (e.g., scratch-resistant) cover and housing substrate, which also has strong optical performance characteristics. Often, the cover substrate includes glass for this purpose; however other substrates may be used.

Strong optical performance in terms of maximum light transmission and minimum reflectivity are required in cover substrate applications (and potentially in some housing substrate applications). Furthermore, cover substrate applications require that the color exhibited or perceived, in reflection and/or transmission, does not change appreciably as the viewing angle (or incident illumination angle) is changed. This is because, if the color, reflectivity or transmission changes with viewing angle to an appreciable degree, the user of the product incorporating the cover glass will perceive a change in the color or brightness of the display, which can diminish the perceived quality of the display. Of these changes, a change in color is often the most noticeable and objectionable to users.

Known cover substrates include glass and film combinations can often exhibit a variety of different types of scratches after use in harsh operating conditions. In some instances, a significant portion of those scratches are microductile scratches, which typically include a single groove in a material having extended length and with depths in the range from about 100 nm to about 500 nm. Microductile scratches may be accompanied by other types of visible damage, such as sub-surface cracking, frictive cracking, chipping and/or wear. Evidence suggests that a majority of such scratches and other visible damage is caused by sharp contact that occurs in a single contact event. Once a significant scratch appears on the cover substrate, the appearance of the product is degraded since the scratch causes an increase in light scattering, which may cause significant reduction in brightness, clarity and contrast of images on the display. Significant scratches can also affect the accuracy and reliability of touch sensitive displays. A portion of such scratches and other visible damage as described above may also be caused by multiple contact events (including reciprocating abrasion or wear). These scratches, and even less significant scratches, are unsightly and can affect product performance.

Single event scratch damage can be contrasted with abrasion damage. Abrasion damage is typically caused by multiple contact events, such as reciprocating sliding contact from hard counter face objects (e.g., sand, gravel and sandpaper). Abrasion damage can generate heat, which can degrade chemical bonds in the film materials and cause flaking and other types of damage to the cover glass. In addition, since abrasion damage is often experienced over a longer term than the single events that cause scratches, the film material experiencing abrasion damage can also oxidize, which further degrades the durability of the film and thus the glass-film laminate. The single events that cause scratches generally do not involve the same conditions as the events that cause abrasion damage and therefore, the solutions often utilized to prevent abrasion damage may not also prevent scratches in cover substrates. Moreover, known scratch and abrasion damage solutions often compromise the optical properties.

Accordingly, there is a need for new cover substrates, and methods for their manufacture, which are scratch resistant over a wide range of different types of scratches, abrasion resistant, and have good optical performance.

SUMMARY

One aspect of the present disclosure pertains to an article including a substrate with a surface and an optical film disposed on the surface of the substrate forming a coated surface. The article of one or more embodiments exhibits a transmittance color and/or reflectance such that the transmittance color coordinates and/or the reflectance color coordinates (measured at the coated surface) have color shift of about 2 or less or a color shift of about 0.5 or less, when viewed at an incident illumination angle in the range from about 0 degrees to about 60 degrees from normal incidence under an illuminant. Exemplary illuminants include International Commission on Illumination (“CIE”) F2 or CIE F10.

The article of some embodiments may exhibit a hardness of about 8 GPa or greater, as measured by a Berkovich Indenter Hardness Test, as described herein, along an indentation depth of about 100 nm or greater (e.g., from about 100 nm to about 300 nm, from about 100 nm to about 400 nm, from about 100 nm to about 500 nm, or from about 100 nm to about 600 nm). The article may optionally include a crack mitigating layer disposed between the optical film and the substrate or within the optical film.

In one or more embodiments, the optical film includes a scratch-resistant layer. The scratch-resistant layer may exhibit a hardness of about 8 GPa or greater, as measured by the Berkovich Indenter Hardness Test. The scratch-resistant layer of some embodiments may exhibit a refractive index of about 1.7 or greater. The scratch-resistant layer may include one or more of AlN, Si₃N₄, AlO_(x)N_(y), SiO_(x)N_(y), Al₂O₃, SixCy, Si_(x)O_(y)C_(z), ZrO₂, TiO_(x)N_(y), diamond, diamond-like carbon, and Si_(u)Al_(v)O_(x)N_(y).

The optical film of one or more embodiments includes an optical interference layer disposed between the scratch-resistant layer and the substrate. The optical interference layer may include a first low refractive index (RI) sub-layer and a second high RI sub-layer. The difference between the refractive index of the first low RI sub-layer and the refractive index of the second high RI sub-layer may be about 0.01 or greater (e.g., about 0.1 or greater, about 0.2 or greater, about 0.3 or greater or about 0.4 or greater). In one or more embodiments, the optical interference layer includes a plurality of sub-layer sets (e.g., up to about 10 sub-layer sets), which can include a first low RI sub-layer and a second high RI sub-layer. The first low RI sub-layer may include one or more of SiO₂, Al₂O₃, GeO₂, SiO, AlO_(x)N_(y), SiO_(x)N_(y), Si_(u)Al_(v)O_(x)N_(y), MgO, MgF₂, BaF₂, CaF₂, DyF₃, YbF₃, YF₃, and CeF₃. The second high RI sub-layer may include at least one of Si_(u)Al_(v)O_(x)N_(y), Ta₂O₅, Nb₂O₅, AlN, Si₃N₄, AlO_(x)N_(y), SiO_(x)N_(y), HfO₂, TiO₂, ZrO₂, Y₂O₃, Al₂O₃, and MoO₃.

In some instances, the optical interference layer includes a third sub-layer. The third sub-layer may be disposed between the plurality of sub-layer sets and the scratch-resistant layer. Alternatively, the third sub-layer may be disposed between the substrate and the plurality of sub-layer sets. The third sub-layer of one or more embodiments may have a RI between the refractive index of the first low RI sub-layer and the refractive index of the second high RI sub-layer. The optical film of some embodiments may include a capping layer disposed on the scratch-resistant layer.

The first low RI sub-layer and/or the second high RI sub-layer of the optical interference layer may have an optical thickness (n*d) in the range from about 2 nm to about 200 nm. The optical interference layer may exhibit a thickness of about 800 nm or less.

In some embodiments, the optical interference layer exhibits an average light reflection of about 0.5% or less over the optical wavelength regime. In some embodiments, the article exhibits an average transmittance or average reflectance having an average oscillation amplitude of about 5 percentage points or less over the optical wavelength regime.

The substrate of one or more embodiments may include an amorphous substrate or a crystalline substrate. The amorphous substrate can include a glass selected from the group consisting of soda lime glass, alkali aluminosilicate glass, alkali containing borosilicate glass and alkali aluminoborosilicate glass. The glass may be optionally chemically strengthened and/or may include a compressive stress (CS) layer with a surface CS of at least 250 MPa extending within the chemically strengthened glass from a surface of the chemically strengthened glass to a depth of layer (DOL). The DOL exhibited by such substrates may be at least about 10 μm.

The articles disclosed herein may include articles with a display (or display articles) (e.g., consumer electronics, including mobile phones, tablets, computers, navigation systems, and the like), architectural articles, transportation articles (e.g., automotive, trains, aircraft, sea craft, etc.), appliance articles, or any article that requires some transparency, scratch-resistance, abrasion resistance or a combination thereof.

Additional features and advantages will be set forth in the detailed description which follows. Additional features and advantages will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments described herein and in the appended drawings.

It is to be understood that both the foregoing general description and the following detailed description are merely exemplary, and are intended to provide an overview or framework to understanding the nature and character of the claims. The accompanying drawings are included to provide a further understanding, and are incorporated in and constitute a part of this specification. The drawings illustrate one or more embodiment(s), and together with the description, serve to explain principles and operation of the various embodiments.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an illustration of a known substrate and a scratch-resistant material embodiment;

FIG. 2 is an illustration of a known article including a single layer interference layer;

FIG. 3 is a reflectance spectra for the article shown in FIG. 2 ;

FIG. 4 is a graph showing the range of calculated a* and b* color shifts based on the reflectance spectra shown in FIG. 3 ;

FIG. 5 is illustration of an article according to one or more embodiments;

FIG. 6 is a more detailed illustration of the article shown in FIG. 5 ;

FIG. 7 is a calculated reflectance spectra for the article having an optical interference layer with three sub-layer sets, according to modeled Example 1;

FIG. 8 is a graph showing the range of calculated a* and b* color shifts for modeled Example 1;

FIG. 9 is a schematic representation of the article according to modeled Example 2;

FIG. 10 is a calculated reflectance spectra for the article according to modeled Example 2;

FIG. 11 is a graph showing the range of calculated a* and b* color shifts for modeled Example 2;

FIG. 12 is a schematic representation of the article according to modeled Example 3;

FIG. 13 is a calculated reflectance spectra for the article according to modeled Example 3;

FIG. 14 is a graph showing the range of calculated a* and b* color shifts for modeled Example 3;

FIG. 15 is a schematic representation of the article according to modeled Example 4;

FIG. 16 is a calculated reflectance spectra for the article according to modeled Example 4;

FIG. 17 is a graph showing the range of calculated a* and b* color shifts for modeled Example 4;

FIG. 18 is a schematic representation of the article according to modeled Example 5;

FIG. 19 is a calculated reflectance spectra for the article according to modeled Example 5;

FIG. 20 is a schematic representation of the article according to modeled Example 6;

FIG. 21 is a calculated reflectance spectra for the article according to modeled Example 6;

FIG. 22 is a schematic representation of the article according to modeled Example 7;

FIG. 23 is a calculated reflectance spectra for the article according to modeled Example 7;

FIG. 24 is a schematic representation of the article according to modeled Example 8;

FIG. 25 is a calculated reflectance spectra for the article according to modeled Example 8;

FIG. 26 is a graph showing the range of calculated a* and b* color shifts for modeled Examples 6-8;

FIG. 27 is a schematic representation of the article according to modeled Example 9;

FIG. 28 is a calculated reflectance spectra for the article according to modeled Example 9;

FIG. 29 shows the measured transmittance spectra for articles according to Examples 10-11 and Comparative Example 12;

FIG. 30 shows the measured reflected color coordinates for Examples 10-11 and bare glass at different incident illumination angles;

FIG. 31 shows the measured transmitted light color coordinates for Examples 10-11 at an incident illumination angle of 5 degrees; and

FIG. 32 is a schematic representation of the article according to modeled Example 13.

DETAILED DESCRIPTION

Reference will now be made in detail to various embodiment(s), examples of which are illustrated in the accompanying drawings. Whenever possible, the same reference numerals will be used throughout the drawings to refer to the same or like parts.

Known scratch-resistant materials, such as AlN, Si₃N₄, AlO_(x)N_(y), and SiO_(x)N_(y), have high refractive indices, for example, in the range from about 1.7 to about 2.1. Common substrates that include scratch-resistant materials are glass and plastic substrates. Glass and plastic materials typically have refractive indices in the range from about 1.45 to about 1.65. This difference in the refractive index of the scratch-resistant materials and the substrate can contribute to undesirable optical interference effects. These undesirable optical interference effects may be more pronounced where the scratch-resistant materials have a physical thickness in the range from about 0.05 to about 10 microns. Optical interference between reflected waves from the scratch-resistant material/air interface 10 (as shown in FIG. 1 ) and the scratch-resistant material/substrate interface 20 (as shown in FIG. 1 ) can lead to spectral reflectance oscillations that create apparent color in the scratch-resistant materials 30 (and/or the combination of the scratch-resistant materials 30 and substrate 40), particularly in reflection. The color shifts in reflection with viewing angle due to a shift in the spectral reflectance oscillations with incident illumination angle. The observed color and color shifts with incident illumination angle are often distracting or objectionable to device users, particularly under illumination with sharp spectral features such as fluorescent lighting and some LED lighting.

Observed color and color shifts can be reduced by minimizing the reflectance at one or both interfaces 10, 20, thus reducing reflectance oscillations and reflected color shifts for the entire article. For scratch-resistant materials, the reduction in reflectance is often most feasible at the scratch-material/substrate interface 20, while simultaneously retaining the high durability or scratch resistance of the scratch-resistant materials/air interface 10. Various ways to reduce reflectance include the use of a single optical interference layer (as shown in FIG. 2 ) or a layer having a monotonic gradient in refractive index at the scratch-resistant material/substrate interface 20. Such options, however, often exhibit large oscillations in the transmittance and/or reflectance spectra under various illuminants. A single layer interference layer is included in the article shown in FIG. 2 . The article includes an alkali aluminoborosilicate glass substrate 10, a single layer interference layer 50 of Al₂O₃ having a physical thickness of about 80 nanometers (nm), an scratch-resistant layer 30 of Si_(u)Al_(v)O_(x)N_(y) having a physical thickness of about 2000 nm, and a layer 60 of SiO₂ having a physical thickness of about 10 nm. FIG. 3 shows a modeled reflectance spectrum for the article illustrated in FIG. 2 . The spectrum exhibits oscillations over the optical wavelength regime having amplitudes in the range from about 3.5 percentage points (e.g., a low reflectance of about 8.5% and a peak reflectance of about 12%, at the wavelength range from about 520 nm to 540 nm) to about 8 percentage points (e.g., a low reflectance of about 6.5% and a peak reflectance to about 14.5%, at the wavelength of about 400 nm to 410 nm). As used herein, the term “amplitude” includes the peak-to-valley change in reflectance or transmittance. As used herein, the term “transmittance” is defined as the percentage of incident optical power within a given wavelength range transmitted through a material (e.g., the article, the substrate or the optical film or portions thereof). The term “reflectance” is similarly defined as the percentage of incident optical power within a given wavelength range that is reflected from a material (e.g., the article, the substrate, or the optical film or portions thereof). Transmittance and reflectance are measured using a specific linewidth. In one or more embodiments, the spectral resolution of the characterization of the transmittance and reflectance is less than 5 nm or 0.02 eV.

The phrase “average amplitude” includes the peak-to-valley change in reflectance or transmittance averaged over every possible 100 nm wavelength range within the optical wavelength regime. As used herein, the “optical wavelength regime” includes the wavelength range from about 420 nm to about 700 nm. From this information, it can be predicted that the article shown in FIGS. 2 and 3 will exhibit relatively large color shifts when viewed at different incident illumination angles from normal incidence under different illuminants, as shown in FIG. 4 .

The embodiments of this disclosure utilize an optical interference layer including multiple layers disposed between the substrate and the scratch-resistant materials. The optical interference layer achieves improved optical performance, in terms of colorlessness and/or smaller color shifts with viewed at varying incident illumination angles from normal incidence under different illuminants. Such optical interference layers are amenable to faster manufacturing over monotonic gradient designs, and articles incorporating optical interference layers provide scratch-resistance and superior optical properties.

A first aspect of this disclosure pertains to an article that exhibits colorlessness even when viewed at different incident illumination angles under an illuminant. In one or more embodiments, the article exhibits a color shift of about 2 or less for any incidental illumination angles in the ranges provided herein. As used herein, the phrase “color shift” refers to the change in both a* and b* values, under the CIE L*, a*, b* colorimetry system, in reflectance or transmittance. The a* and b* values are described as transmittance color (or transmittance color coordinates) or reflectance color (or reflectance color coordinates), respectively. Color shift may be determined using the following equation: √((a*₂−a*₁)²+(b*₂−b*₁)²), a* and b* coordinates (in transmittance or reflectance) of the article when viewed at normal incidence (i.e., a*₁, and b*₁) and at an incident illumination angle away from normal incidence (i.e., a*₂, and b*₂), provided that the incident illumination angle is different from normal incidence and in some cases differs from normal incidence by at least about 2 degrees or about 5 degrees. Measurements of the various colors over a collection of different observers indicates that the average observer sees a just-noticeable difference in the two colors when the color shift is of about 2.

In some instances, a color shift of about 2 or less is exhibited by the article when viewed at various incident illumination angles from normal incidence, under an illuminant. In some instances the color shift is about 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, 1.1 or less, 1 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.3 or less, 0.2 or less, or 0.1 or less. In some embodiments, the color shift may be about 0. The illuminant can include standard illuminants as determined by the CIE, including A illuminants (representing tungsten-filament lighting), B illuminants (representing daylight simulating illuminants), C illuminants (representing daylight simulating illuminants), D series illuminants (representing natural daylight), and F series illuminants (representing various types of fluorescent lighting). In specific examples, the articles exhibit a color shift of about 2 or less when viewed at incident illumination angle from normal incidence under a CIE F2, F10, F11, F12 or D65 illuminant. The incident illumination angle may be in the range from about 0 degrees to about 80 degrees, from about 0 degrees to about 75 degrees, from about 0 degrees to about 70 degrees, from about 0 degrees to about 65 degrees, from about 0 degrees to about 60 degrees, from about 0 degrees to about 55 degrees, from about 0 degrees to about 50 degrees, from about 0 degrees to about 45 degrees, from about 0 degrees to about 40 degrees, from about 0 degrees to about 35 degrees, from about 0 degrees to about 30 degrees, from about 0 degrees to about 25 degrees, from about 0 degrees to about 20 degrees, from about 0 degrees to about 15 degrees, from about 5 degrees to about 80 degrees, from about 5 degrees to about 80 degrees, from about 5 degrees to about 70 degrees, from about 5 degrees to about 65 degrees, from about 5 degrees to about 60 degrees, from about 5 degrees to about 55 degrees, from about 5 degrees to about 50 degrees, from about 5 degrees to about 45 degrees, from about 5 degrees to about 40 degrees, from about 5 degrees to about 35 degrees, from about 5 degrees to about 30 degrees, from about 5 degrees to about 25 degrees, from about 5 degrees to about 20 degrees, from about 5 degrees to about 15 degrees, and all ranges and sub-ranges therebetween, away from normal incidence. The article may exhibit the maximum color shifts described herein at and along all the incident illumination angles in the range from about 0 degrees to about 80 degrees away from normal incidence. In one example, the article may exhibit a color shift of 2 or less at any incident illumination angle in the range from about 0 degrees to about 60 degrees, from about 2 degrees to about 60 degrees, or from about 5 degrees to about 60 degrees away from normal incidence.

According to one or more embodiments, the article 100 exhibits an average transmittance of 85% or greater over the visible spectrum. In one or more embodiments, the article 100 has a total reflectance of 15% or less.

Referring to FIG. 5 , the article 100 according to one or more embodiments may include a substrate 110, and an optical film 120 disposed on the substrate. The substrate 110 includes opposing major surfaces 112, 114 and opposing minor surfaces 116, 118. The optical film 120 is shown in FIG. 5 as being disposed on a first opposing major surface 112; however, the optical film 120 may be disposed on the second opposing major surface 114 and/or one or both of the opposing minor surfaces, in addition to or instead of being disposed on the first opposing major surface 112. The article 100 includes a coated surface 101.

The optical film 120 includes at least one layer of at least one material. The term “layer” may include a single layer or may include one or more sub-layers. Such sub-layers may be in direct contact with one another. The sub-layers may be formed from the same material or two or more different materials. In one or more alternative embodiments, such sub-layers may have intervening layers of different materials disposed therebetween. In one or more embodiments a layer may include one or more contiguous and uninterrupted layers and/or one or more discontinuous and interrupted layers (i.e., a layer having different materials formed adjacent to one another). A layer or sub-layers may be formed by any known method in the art, including discrete deposition or continuous deposition processes. In one or more embodiments, the layer may be formed using only continuous deposition processes, or, alternatively, only discrete deposition processes.

As used herein, the term “dispose” includes coating, depositing and/or forming a material onto a surface using any known method in the art. The disposed material may constitute a layer, as defined herein. The phrase “disposed on” includes the instance of forming a material onto a surface such that the material is in direct contact with the surface and also includes the instance where the material is formed on a surface, with one or more intervening material(s) is between the disposed material and the surface. The intervening material(s) may constitute a layer, as defined herein.

The articles described herein have scratch resistance, which may be characterized by a measured hardness of the article (or the measured hardness of the optical film, which may include a scratch resistant layer, as described herein). Hardness may be measured by a “Berkovich Indenter Hardness Test”, which includes measuring the hardness of a material on a surface thereof by indenting the surface with a diamond Berkovich indenter. The Berkovich Indenter Hardness Test includes indenting the coated surface 101 of the article or the surface of the optical film (which may include the scratch resistant layer, described herein) with the diamond Berkovich indenter to form an indent to an indentation depth in the range from about 50 nm to about 1000 nm (or the entire thickness of the optical film, whichever is less) and measuring the maximum hardness from this indentation along the entire indentation depth range or a segment of this indentation depth (e.g., in the range from about 100 nm to about 600 nm), generally using the methods set forth in Oliver, W. C.; Pharr, G. M. An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments. J. Mater. Res., Vol. 7, No. 6, 1992, 1564-1583; and Oliver, W. C.; Pharr, G. M. Measurement of Hardness and Elastic Modulus by Instrument Indentation: Advances in Understanding and Refinements to Methodology., J. Mater. Res., Vol. 19, No. 1, 2004, 3-20. The indentation depth is made and measured from the coated surface 101 of the article, the surface of the optical film and/or surface of any one or more of the layers in the optical film. As used herein, hardness refers to a maximum hardness, and not an average hardness.

Typically in nanoindentation measurement methods (such as by using a Berkovich indenter) of a coating or film that is harder than the underlying substrate, the measured hardness may appear to increase initially due to development of the plastic zone at shallow indentation depths and then increases and reaches a maximum value or plateau at deeper indentation depths. Thereafter, hardness begins to decrease at even deeper indentation depths due to the effect of the underlying substrate. Where a substrate having an increased hardness compared to the coating is utilized, the same effect can be seen; however, the hardness increases at deeper indentation depths due to the effect of the underlying substrate.

The indentation depth range and the hardness values at certain indentation depth range(s) can be selected to identify a particular hardness response of the optical film and layers thereof, described herein, without the effect of the underlying substrate. When measuring hardness of the optical film or layers thereof (when disposed on a substrate) with a Berkovich indenter, the region of permanent deformation (plastic zone) of a material is associated with the hardness of the material. During indentation, an elastic stress field extends well beyond this region of permanent deformation. As indentation depth increases, the apparent hardness and modulus are influenced by stress field interactions with the underlying substrate. The substrate influence on hardness occurs at deeper indentation depths (i.e., typically at depths greater than about 10% of the optical film structure or layer thickness). Moreover, a further complication is that the hardness response requires a certain minimum load to develop full plasticity during the indentation process. Prior to that certain minimum load, the hardness shows a generally increasing trend.

At small indentation depths (which also may be characterized as small loads) (e.g., up to about 100 nm, or less than about 70 nm), the apparent hardness of a material appears to increase dramatically versus indentation depth. This small indentation depth regime does not represent a true metric of hardness but instead, reflects the development of the aforementioned plastic zone, which is related to the finite radius of curvature of the indenter. At intermediate indentation depths, the apparent hardness approaches maximum levels. At deeper indentation depths, the influence of the substrate becomes more pronounced as the indentation depths increase. Hardness may begin to drop dramatically once the indentation depth exceeds about 30% of the optical film structure thickness or the layer thickness.

It has been observed that the hardness measured at intermediate indentation depths (at which hardness approaches and is maintained at maximum levels) and at deeper indentation depths depends on the thickness of a material or layer. Specifically, the hardness response of four different layers (i.e., 500 nm thick, 1000 nm thick, 1500 nm thick, and 2000 nm thick) of AlO_(x)N_(y) having different thicknesses was evaluated. The hardness of each layer was measured using the Berkovich Indenter Hardness Test. The 500 nm-thick layer exhibited its maximum hardness at indentation depths from about 100 nm to 180 nm, followed by a dramatic decrease in hardness at indentation depths from about 180 nm to about 200 nm, indicating the hardness of the substrate influencing the hardness measurement. The 1000 nm-thick layer exhibited a maximum hardness at indentation depths from about 100 nm to about 300 nm, followed by a dramatic decrease in hardness at indentation depths greater than about 300 nm. The 1500 nm-thick layer exhibited a maximum hardness at indentation depths from about 100 nm to about 550 nm and the 2000-nm thick layer exhibited a maximum hardness at indentation depths from about 100 nm to about 600 nm.

In some embodiments, the article, the optical film and/or layer(s) in the optical film exhibit a maximum hardness at indentation depths greater than about 100 nm or greater than about 200 nm and thus exhibit sufficient hardness to provide scratch resistance, that is not influenced by the substrate. In some embodiments, the article, the optical film and/or layer(s) in the optical film have a maximum hardness at such indentation depths and thus are resistant to specific scratches such as microductile scratches (which typically have depths of about 100 nm to about 500 nm or from about 200 nm to about 400 nm). For example, the coated surface 101 (or the surface of the optical film or any one or more layers of the optical film) may be resistant to microductile scratches because the article exhibits the hardness values recited herein along specific indentation depths, as measured by a Berkovich Indenter Hardness Test.

The measured or apparent hardness of the article and/or optical film (or layers in the optical film) may be maximized by tuning the thickness of the optical film or one or more layer(s) in the optical film.

In one or more embodiments, the article 100 exhibits an average hardness of about 8 GPa or greater, about 10 GPa or greater, about 14 GPa or greater, about 18 GPa or greater, as measured by the Berkovich Indenter Hardness test. In some embodiments, the average hardness of the article may be in the range from about 5 GPa to about 30 GPa, from about 6 GPa to about 30 GPa, from about 7 GPa to about 30 GPa, from about 8 GPa to about 30 GPa, from about 9 GPa to about 30 GPa, from about 10 GPa to about 30 GPa, from about 12 GPa to about 30 GPa, from about 5 GPa to about 28 GPa, from about 5 GPa to about 26 GPa, from about 5 GPa to about 24 GPa, from about 5 GPa to about 22 GPa, from about 5 GPa to about 20 GPa, from about 12 GPa to about 25 GPa, from about 15 GPa to about 25 GPa, from about 16 GPa to about 24 GPa, from about 18 GPa to about 22 GPa and all ranges and sub-ranges therebetween. These hardness values may be present at indentation depths of about 50 nm or greater, or about 100 nm or greater (e.g., (e.g., from about 100 nm to about 300 nm, from about 100 nm to about 400 nm, from about 100 nm to about 500 nm, from about 100 nm to about 600 nm, from about 200 nm to about 300 nm, from about 200 nm to about 400 nm, from about 200 nm to about 500 nm, or from about 200 nm to about 600 nm).

In one or more embodiments, article 100 also exhibits abrasion resistance. Specifically, one or more embodiments of the articles described herein exhibit resistance to scratches and other damage formed by abrasion (or multiple contact events). Various forms of abrasion test are known in the art, such as that specified in ASTM D1044-99, using abrasive media supplied by Taber Industries. Modified abrasion methods related to ASTM D 1044-99 can be created using different types of abrading media, abradant geometry and motion, pressure, etc. in order to provide repeatable and measurable abrasion or wear tracks to meaningfully differentiate the abrasion resistance of different samples. For example, different test conditions will usually be appropriate for soft plastics vs. hard inorganic test samples. The embodiments described herein exhibit scratch resistance as measured by a specific modified version of the ASTM D 1044-99 test referred to herein as the “Taber Test”, or a “Garnet Test”, which provide clear and repeatable differentiation of durability between different samples, which comprise primarily hard inorganic materials. These test methods may generate a combination of micro-ductile scratches together with other damage modes mentioned above, depending on the specific sample tested.

As used herein, the phrase “Taber Test” refers to a test method using a Taber Linear Abraser 5750 (TLA 5750) and accessories supplied by Taber Industries, in an environment including a temperature of about 22° C.±3° C. and Relative Humidity of up to about 70%. The TLA 5750 includes a CS-17 abraser material having a 6.7 mm diameter abraser head. Each sample was abraded according to the Taber Test and the abrasive damage was evaluated using both Haze and Bidirectional Transmittance Distribution Function (BTDF) measurements, among other methods. In the Taber Test, the procedure for abrading each sample includes placing the TLA 5750 and a flat sample support on a rigid, flat surface and securing the TLA 5750 and the sample support to the surface. Before each sample is abraded under the Taber Test, the abraser material (CS-17) is refaced using a new S-14 refacing strip adhered to glass. The abraser is subjected to 10 refacing cycles using a cycle speed of 25 cycles/minute and stroke length of 1 inch, with no additional weight added (i.e., a total weight of about 350 g is used during refacing, which is the combined weight of the spindle and collet holding the abraser). The procedure then includes operating the TLA 5750 to abrade the sample, where the sample is placed in the sample support in contact with the abraser head and supporting the weight applied to the abraser head, using a cycle speed of 25 cycles/minute, and a stroke length of 1 inch, and a weight such that the total weight applied to the sample is 850 g (i.e., a 500 g auxiliary weight is applied in addition to the 350 g combined weight of the spindle and collet). The procedure includes forming two wear tracks on each sample for repeatability, and abrading each sample for 500 cycle counts in each of the two wear tracks on each sample.

In one or more embodiments, the coated surface 101 of the article is abraded according to the above Taber Test and the article exhibits a haze of about 5% or less, as measured on the abraded side using a hazemeter supplied by BYK Gardner under the trademark Haze-Gard Plus®, using an aperture over the source port, the aperture having a diameter of 8 mm.

In some embodiments, the haze measured after the Taber Test may be about 4% or less, about 3% or less, about 2% or less, about 1% or less, about 0.8% or less, about 0.5% or less, about 0.4% or less, about 0.3%, about 0.2% or less, or about 0.1% or less.

In one or more embodiments, the coated surface 101 of the article may exhibit an abrasion resistance, after being abraded by the Taber Test as measured by a light scattering measurement. In one or more embodiments, the light scattering measurement includes a bi-directional reflectance distribution function (BRDF) or bi-directional transmittance distribution function (BTDF) measurement carried out using a Radiant Zemax IS-SA™ instrument. This instrument has the flexibility to measure light scattering using any input angle from normal to about 85 degrees incidence in reflection, and from normal to about 85 degrees incidence in transmission, while also capturing all scattered light output in either reflection or transmission into 2*Pi steradians (a full hemisphere in reflection or transmission). In one embodiment, the article 100 exhibits an abrasion resistance, as measured using BTDF at normal incidence and analyzing the transmitted scattered light at a selected angular range, for example from about 10° to about 80° degrees in polar angles and any angular range therein. The full azimuthal range of angles can be analyzed and integrated, or particular azimuthal angular slices can be selected, for example from about 0° and 90° azimuthally. In the case of linear abrasion an azimuthal direction that is substantially orthogonal to the abrasion direction may be utilized so as to increase signal-to-noise of the optical scattering measurement. In one or more embodiments, the article may exhibit a scattered light intensity after the Taber Test as measured at the coated surface 101, of about less than about 0.1, about 0.05 or less, about 0.03 or less, about 0.02 or less, about 0.01 or less, about 0.005 or less, or about 0.003 or less (in units of 1/steradian), when using the Radiant Zemax IS-SA tool in CCBTDF mode at normal incidence in transmission, with a 2 mm aperture and a monochrometer set to 600 nm wavelength, and when evaluated at polar scattering angles in the range from about 15° to about 60° (e.g. specifically, about 20°). Normal incidence in transmission may be otherwise known as zero degrees in transmission, which may be denoted as 180° incidence by the instrument software. In one or more embodiments, the scattered light intensity may be measured along an azimuthal direction substantially orthogonal to the abraded direction of a sample abraded by the Taber Test. These optical intensity values may also correspond to less than about 1%, less than about 0.5%, less than about 0.2%, or less than about 0.1% of the input light intensity that is scattered into polar scattering angles greater than about 5 degrees, greater than about 10 degrees, greater than about 30 degrees, or greater than about 45 degrees.

Generally speaking, BTDF testing at normal incidence, as described herein, is closely related to the transmission haze measurement, in that both are measuring the amount of light that is scattered in transmission through a sample (or, in this case the article, after abrading the coated surface 101). BTDF measurements provide more sensitivity as well as more detailed angular information, compared to haze measurements. BTDF allows measurement of scattering into different polar and azimuthal angles, for example allowing us to selectively evaluate the scattering into azimuthal angles that are substantially orthogonal to the abrasion direction in the linear Taber test (these are the angles where light scattering from linear abrasion is the highest). Transmission haze is essentially the integration of all scattered light measured by normal incidence BTDF into the entire hemisphere of polar angles greater than about +/−2.5 degrees.

The Garnet Test uses the same apparatus as the Taber Test (i.e., a Taber linear abraser, or an equivalent apparatus). The Garnet Test includes using a 150-grit garnet sandpaper to abrade the sample surface under varying applied loads for one reciprocation cycle (i.e., one forward-and-back cycle), with a stroke length of 1″ and a speed of 45 cycles/minute. The loads applied are in terms of a total load (including the weight of the abraser spindle, holder, and any added weights). The garnet sandpaper has a contact area with the samples of about 7 mm, similar to the Taber test. The Garnet Test performed in this way is generally more aggressive than the Taber Test and can produce a wider variety of damage modes. The visible scratches and damage are also more random. Light scattering from these samples can be characterized using BTDF and Haze measurements as described above.

In one or more embodiments, the article exhibits a haze of about 3% or less (e.g., about 2% or less, about 1% or less, about 0.5% or less, or about 0.2% or less) after the Garnet Test, when tested in the Garnet Test with a total load in the range from about 380 g to about 2100 g. The articles of one or more embodiment exhibit a scattered light level at a polar angle of 20 degrees (orthogonal to abrasion axis, as measured by CC-BTDF) of about 0.04 or less, about 0.02 or less, about 0.01 or less, or even about 0.005 or less, in units of 1/steradian.

According to one or more embodiments, the article 100 exhibits an average light transmission of about 80% or greater. The term “light transmission” refers to the amount of light that is transmitted through a medium. The measure of light transmission is the difference between the amount of light that enters the medium and the amount of light that exits the medium. In other words, light transmission is the light that has traveled through a medium without being absorbed or scattered. The term “average light transmission” refers to spectral average of the light transmission multiplied by the luminous efficiency function, as described by CIE standard observer. The article 100 of specific embodiments may exhibit an average light transmission of 80% or greater, 82% or greater, 85% or greater, 90% or greater, 90.5% or greater, 91% or greater, 91.5% or greater, 92% or greater, 92.5% or greater, 93% or greater, 93.5% or greater, 94% or greater, 94.5% or greater, or 95% or greater.

In one or more embodiments, the article 100 has a total reflectivity that 20% or less. For example, the article may have a total reflectivity of 20% or less, 15%, or less, 10% or less, 9% or less, 8% or less, 7% or less, 6% or less. In some specific embodiments, the article has a total reflectivity of 6.9% or less, 6.8% or less, 6.7% or less, 6.6% or less, 6.5% or less, 6.4% or less, 6.3% or less, 6.2% or less, 6.1% or less, 6.0% or less, 5.9% or less, 5.8% or less, 5.7% or less, 5.6% or less, or 5.5% or less. In accordance with one or more embodiments, the article 100 has a total reflectivity that is the same or less than the total reflectivity of the substrate 110. In one or more embodiments, the article 100 exhibits a relatively flat transmittance spectrum, reflectance spectrum or transmittance and reflectance spectrum over the optical wavelength regime. In some embodiments, the relatively flat transmittance and/or reflectance spectrum includes an average oscillation amplitude of about 5 percentage points or less along the entire optical wavelength regime or wavelength range segments in the optical wavelength regime. Wavelength range segments may be about 50 nm, about 100 nm, about 200 nm or about 300 nm. In some embodiments, the average oscillation amplitude may be about 4.5 percentage points or less, about 4 percentage points or less, about 3.5 percentage points or less, about 3 percentage points or less, about 2.5 percentage points or less, about 2 percentage points or less, about 1.75 percentage points or less, about 1.5 percentage points or less, about 1.25 percentage points or less, about 1 percentage point or less, about 0.75 percentage points or less, about 0.5 percentage points of less, about 0.25 percentage points or less, or about 0 percentage points, and all ranges and sub-ranges therebetween. In one or more specific embodiments, the article exhibits a transmittance over a selected wavelength range segment of about 100 nm or 200 nm over the optical wavelength regime, wherein the oscillations from the spectra have a maximum peak of about 80%, about 82%, about 84%, about 86%, about 87%, about 88%, about 89%, about 90%, about 91%, about 92%, about 93%, about 94%, or about 95%, and all ranges and sub-ranges therebetween.

In some embodiments, the relatively flat average transmittance and/or average reflectance includes maximum oscillation amplitude, expressed as a percent of the average transmittance or average reflectance, along a specified wavelength range segment in the optical wavelength regime. The average transmittance or average reflectance would also be measured along the same specified wavelength range segment in the optical wavelength regime. The wavelength range segment may be about 50 nm, about 100 nm or about 200 nm. In one or more embodiments, the article 100 exhibits an average transmittance and/or average reflectance with an average oscillation amplitude of about 10% or less, about 5% or less, about 4.5% of less, about 4% or less, about 3.5% or less, about 3% or less, about 2.5% or less, about 2% or less, about 1.75% or less, about 1.5% or less, about 1.25% or less, about 1% or less, about 0.75% or less, about 0.5% or less, about 0.25% or less, or about 0.1% or less, and all ranges and sub-ranges therebetween. Such percent-based average oscillation amplitude may be exhibited by the article along wavelength ranges segments of about 50 nm, about 100 nm, about 200 nm or about 300 nm, in the optical wavelength regime. For example, an article may exhibit an average transmittance of about 85% along the wavelength range from about 500 nm to about 600 nm, which is a wavelength range segment of about 100 nm, within the optical wavelength regime. The article may also exhibit a percent-based oscillation amplitude of about 3% along the same wavelength range (500 nm to about 600 nm), which means that along the wavelength range from 500 nm to 600 nm, the absolute (non-percent-based) oscillation amplitude is about 2.55 percentage points.

Substrate

The substrate 110 may be inorganic and may include an amorphous substrate, a crystalline substrate or a combination thereof. The substrate 110 may be formed from man-made materials and/or naturally occurring materials. In some specific embodiments, the substrate 110 may specifically exclude plastic and/or metal substrates. In some embodiments, the substrate 110 may be organic and specifically polymeric. Examples of suitable polymers include, without limitation: thermoplastics including polystyrene (PS) (including styrene copolymers and blends), polycarbonate (PC) (including copolymers and blends), polyesters (including copolymers and blends, including polyethyleneterephthalate and polyethyleneterephthalate copolymers), polyolefins (PO) and cyclicpolyolefins (cyclic-PO), polyvinylchloride (PVC), acrylic polymers including polymethyl methacrylate (PMMA) (including copolymers and blends), thermoplastic urethanes (TPU), polyetherimide (PEI) and blends of these polymers with each other. Other exemplary polymers include epoxy, styrenic, phenolic, melamine, and silicone resins.

In one or more embodiments, the substrate exhibits a refractive index in the range from about 1.45 to about 1.55. In specific embodiments, the substrate 110 may exhibit an average strain-to-failure at a surface on one or more opposing major surface that is 0.5% or greater, 0.6% or greater, 0.7% or greater, 0.8% or greater, 0.9% or greater, 1% or greater, 1.1% or greater, 1.2% or greater, 1.3% or greater, 1.4% or greater 1.5% or greater or even 2% or greater, as measured using ball-on-ring testing using at least 5, at least 10, at least 15, or at least 20 samples. In specific embodiments, the substrate 110 may exhibit an average strain-to-failure at its surface on one or more opposing major surface of about 1.2%, about 1.4%, about 1.6%, about 1.8%, about 2.2%, about 2.4%, about 2.6%, about 2.8%, or about 3% or greater.

Suitable substrates 110 may exhibit an elastic modulus (or Young's modulus) in the range from about 30 GPa to about 120 GPa. In some instances, the elastic modulus of the substrate may be in the range from about 30 GPa to about 110 GPa, from about 30 GPa to about 100 GPa, from about 30 GPa to about 90 GPa, from about 30 GPa to about 80 GPa, from about 30 GPa to about 70 GPa, from about 40 GPa to about 120 GPa, from about 50 GPa to about 120 GPa, from about 60 GPa to about 120 GPa, from about 70 GPa to about 120 GPa, and all ranges and sub-ranges therebetween.

In one or more embodiments, the substrate may be amorphous and may include glass, which may be strengthened or non-strengthened. Examples of suitable glass include soda lime glass, alkali aluminosilicate glass, alkali containing borosilicate glass and alkali aluminoborosilicate glass. In some variants, the glass may be free of lithia. In one or more alternative embodiments, the substrate 110 may include crystalline substrates such as glass ceramic substrates (which may be strengthened or non-strengthened) or may include a single crystal structure, such as sapphire. In one or more specific embodiments, the substrate 110 includes an amorphous base (e.g., glass) and a crystalline cladding (e.g., sapphire layer, a polycrystalline alumina layer and/or or a spinel (MgAl₂O₄) layer).

The substrate 110 may be substantially planar or sheet-like, although other embodiments may utilize a curved or otherwise shaped or sculpted substrate. The substrate 110 may be substantially optically clear, transparent and free from light scattering. In such embodiments, the substrate may exhibit an average light transmission over the optical wavelength regime of about 85% or greater, about 86% or greater, about 87% or greater, about 88% or greater, about 89% or greater, about 90% or greater, about 91% or greater or about 92% or greater. In one or more alternative embodiments, the substrate 110 may be opaque or exhibit an average light transmission over the optical wavelength regime of less than about 10%, less than about 9%, less than about 8%, less than about 7%, less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, less than about 1%, or less than about 0%. In substrate 110 may optionally exhibit a color, such as white, black, red, blue, green, yellow, orange etc.

Additionally or alternatively, the physical thickness of the substrate 110 may vary along one or more of its dimensions for aesthetic and/or functional reasons. For example, the edges of the substrate 110 may be thicker as compared to more central regions of the substrate 110. The length, width and physical thickness dimensions of the substrate 110 may also vary according to the application or use of the article 100.

The substrate 110 may be provided using a variety of different processes. For instance, where the substrate 110 includes an amorphous substrate such as glass, various forming methods can include float glass processes and down-draw processes such as fusion draw and slot draw.

Once formed, a substrate 110 may be strengthened to form a strengthened substrate. As used herein, the term “strengthened substrate” may refer to a substrate that has been chemically strengthened, for example through ion-exchange of larger ions for smaller ions in the surface of the substrate. However, other strengthening methods known in the art, such as thermal tempering, or utilizing a mismatch of the coefficient of thermal expansion between portions of the substrate to create compressive stress and central tension regions, may be utilized to form strengthened substrates.

Where the substrate is chemically strengthened by an ion exchange process, the ions in the surface layer of the substrate are replaced by—or exchanged with—larger ions having the same valence or oxidation state. Ion exchange processes are typically carried out by immersing a substrate in a molten salt bath containing the larger ions to be exchanged with the smaller ions in the substrate. It will be appreciated by those skilled in the art that parameters for the ion exchange process, including, but not limited to, bath composition and temperature, immersion time, the number of immersions of the substrate in a salt bath (or baths), use of multiple salt baths, additional steps such as annealing, washing, and the like, are generally determined by the composition of the substrate and the desired compressive stress (CS), depth of compressive stress layer (or depth of layer) of the substrate that result from the strengthening operation. By way of example, ion exchange of alkali metal-containing glass substrates may be achieved by immersion in at least one molten bath containing a salt such as, but not limited to, nitrates, sulfates, and chlorides of the larger alkali metal ion. The temperature of the molten salt bath typically is in a range from about 380° C. up to about 450° C., while immersion times range from about 15 minutes up to about 40 hours. However, temperatures and immersion times different from those described above may also be used.

In addition, non-limiting examples of ion exchange processes in which glass substrates are immersed in multiple ion exchange baths, with washing and/or annealing steps between immersions, are described in U.S. patent application Ser. No. 12/500,650, filed Jul. 10, 2009, by Douglas C. Allan et al., entitled “Glass with Compressive Surface for Consumer Applications” and claiming priority from U.S. Provisional Patent Application No. 61/079,995, filed Jul. 11, 2008, in which glass substrates are strengthened by immersion in multiple, successive, ion exchange treatments in salt baths of different concentrations; and U.S. Pat. No. 8,312,739, by Christopher M. Lee et al., issued on Nov. 20, 2012, and entitled “Dual Stage Ion Exchange for Chemical Strengthening of Glass,” and claiming priority from U.S. Provisional Patent Application No. 61/084,398, filed Jul. 29, 2008, in which glass substrates are strengthened by ion exchange in a first bath is diluted with an effluent ion, followed by immersion in a second bath having a smaller concentration of the effluent ion than the first bath. The contents of U.S. patent application Ser. No. 12/500,650 and U.S. Pat. No. 8,312,739 are incorporated herein by reference in their entirety.

The degree of chemical strengthening achieved by ion exchange may be quantified based on the parameters of central tension (CT), surface CS, and depth of layer (DOL). Surface CS may be measured near the surface or within the strengthened glass at various depths. A maximum CS value may include the measured CS at the surface (CS_(s)) of the strengthened substrate. The CT, which is computed for the inner region adjacent the compressive stress layer within a glass substrate, can be calculated from the CS, the physical thickness t, and the DOL. CS and DOL are measured using those means known in the art. Such means include, but are not limited to, measurement of surface stress (FSM) using commercially available instruments such as the FSM-6000, manufactured by Luceo Co., Ltd. (Tokyo, Japan), or the like, and methods of measuring CS and DOL are described in ASTM 1422C-99, entitled “Standard Specification for Chemically Strengthened Flat Glass,” and ASTM 1279.19779 “Standard Test Method for Non-Destructive Photoelastic Measurement of Edge and Surface Stresses in Annealed, Heat-Strengthened, and Fully-Tempered Flat Glass,” the contents of which are incorporated herein by reference in their entirety. Surface stress measurements rely upon the accurate measurement of the stress optical coefficient (SOC), which is related to the birefringence of the glass substrate. SOC in turn is measured by those methods that are known in the art, such as fiber and four point bend methods, both of which are described in ASTM standard C770-98 (2008), entitled “Standard Test Method for Measurement of Glass Stress-Optical Coefficient,” the contents of which are incorporated herein by reference in their entirety, and a bulk cylinder method. The relationship between CS and CT is given by the expression (1):

CT=(CS·DOL)/(t−2DOL)  (1),

wherein t is the physical thickness (μm) of the glass article. In various sections of the disclosure, CT and CS are expressed herein in megaPascals (MPa), physical thickness t is expressed in either micrometers (μm) or millimeters (mm) and DOL is expressed in micrometers (m).

In one embodiment, a strengthened substrate 110 can have a surface CS of 250 MPa or greater, 300 MPa or greater, e.g., 400 MPa or greater, 450 MPa or greater, 500 MPa or greater, 550 MPa or greater, 600 MPa or greater, 650 MPa or greater, 700 MPa or greater, 750 MPa or greater or 800 MPa or greater. The strengthened substrate may have a DOL of 10 μm or greater, 15 μm or greater, 20 μm or greater (e.g., 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm or greater) and/or a CT of 10 MPa or greater, 20 MPa or greater, 30 MPa or greater, 40 MPa or greater (e.g., 42 MPa, 45 MPa, or 50 MPa or greater) but less than 100 MPa (e.g., 95, 90, 85, 80, 75, 70, 65, 60, 55 MPa or less). In one or more specific embodiments, the strengthened substrate has one or more of the following: a surface CS greater than 500 MPa, a DOL greater than 15 μm, and a CT greater than 18 MPa.

Example glasses that may be used in the substrate may include alkali aluminosilicate glass compositions or alkali aluminoborosilicate glass compositions, though other glass compositions are contemplated. Such glass compositions are capable of being chemically strengthened by an ion exchange process. One example glass composition comprises SiO₂, B₂O₃ and Na₂O, where (SiO₂+B₂O₃)≥66 mol. %, and Na₂O≥9 mol. %. In an embodiment, the glass composition includes at least 6 wt. % aluminum oxide. In a further embodiment, the substrate includes a glass composition with one or more alkaline earth oxides, such that a content of alkaline earth oxides is at least 5 wt. %. Suitable glass compositions, in some embodiments, further comprise at least one of K₂O, MgO, and CaO. In a particular embodiment, the glass compositions used in the substrate can comprise 61-75 mol. % SiO2; 7-15 mol. % Al₂O₃; 0-12 mol. % B₂O₃; 9-21 mol. % Na₂O; 0-4 mol. % K₂O; 0-7 mol. %≤MgO; and 0-3 mol. % CaO.

A further example glass composition suitable for the substrate comprises: 60-70 mol. % SiO₂; 6-14 mol. % Al₂O₃; 0-15 mol. % B₂O₃; 0-15 mol. % Li₂O; 0-20 mol. % Na₂O; 0-10 mol. % K₂O; 0-8 mol. % MgO; 0-10 mol. % CaO; 0-5 mol. % ZrO₂; 0-1 mol. % SnO₂; 0-1 mol. % CeO₂; less than 50 ppm As₂O₃; and less than 50 ppm Sb₂O₃; where 12 mol. %≤(Li₂O+Na₂O+K₂O)≤20 mol. % and 0 mol. %≤(MgO+CaO)≤10 mol. %.

A still further example glass composition suitable for the substrate comprises: 63.5-66.5 mol. % SiO₂; 8-12 mol. % Al₂O₃; 0-3 mol. % B₂O₃; 0-5 mol. % Li₂O; 8-18 mol. % Na₂O; 0-5 mol. % K₂O; 1-7 mol. % MgO; 0-2.5 mol. % CaO; 0-3 mol. % ZrO₂; 0.05-0.25 mol. % SnO₂; 0.05-0.5 mol. % CeO₂; less than 50 ppm As₂O₃; and less than 50 ppm Sb₂O₃; where 14 mol. % (Li₂O+Na₂O+K₂O) 18 mol. % and 2 mol. % (MgO+CaO) 7 mol. %.

In a particular embodiment, an alkali aluminosilicate glass composition suitable for the substrate comprises alumina, at least one alkali metal and, in some embodiments, greater than 50 mol. % SiO₂, in other embodiments at least 58 mol. % SiO₂, and in still other embodiments at least 60 mol. % SiO₂, wherein the ratio

${\frac{{Al_{2}O_{3}} + {B_{2}O_{3}}}{\sum{modifiers}} > 1},$

where in the ratio the components are expressed in mol. % and the modifiers are alkali metal oxides. This glass composition, in particular embodiments, comprises: 58-72 mol. % SiO₂; 9-17 mol. % Al₂O₃; 2-12 mol. % B₂O₃; 8-16 mol. % Na₂O; and 0-4 mol. % K₂O, wherein the ratio

$\frac{{Al_{2}O_{3}} + {B_{2}O_{3}}}{\sum{modifiers}} > 1.$

In still another embodiment, the substrate may include an alkali aluminosilicate glass composition comprising: 64-68 mol. % SiO₂; 12-16 mol. % Na₂O; 8-12 mol. % Al₂O₃; 0-3 mol. % B₂O₃; 2-5 mol. % K₂O; 4-6 mol. % MgO; and 0-5 mol. % CaO, wherein: 66 mol. % SiO₂+B₂O₃+CaO 69 mol. %; Na₂O+1(20+B₂O₃+MgO+CaO+SrO>10 mol. %; 5 mol. %≤MgO+CaO+SrO≤8 mol. %; (Na₂O+B₂O₃)— Al₂O₃≤2 mol. %; 2 mol. % Na₂O—Al₂O₃≤6 mol. %; and 4 mol. % (Na₂O+K₂O)—Al₂O₃≤10 mol. %.

In an alternative embodiment, the substrate may comprise an alkali aluminosilicate glass composition comprising: 2 mol % or more of Al₂O₃ and/or ZrO₂, or 4 mol % or more of Al₂O₃ and/or ZrO₂.

Where the substrate 110 includes a crystalline substrate, the substrate may include a single crystal, which may include Al₂O₃. Such single crystal substrates are referred to as sapphire. Other suitable materials for a crystalline substrate include polycrystalline alumina layer and/or spinel (MgAl₂O₄).

Optionally, the crystalline substrate 110 may include a glass ceramic substrate, which may be strengthened or non-strengthened. Examples of suitable glass ceramics may include Li₂O—Al₂O₃—SiO₂ system (i.e. LAS-System) glass ceramics, MgO—Al₂O₃—SiO₂ system (i.e. MAS-System) glass ceramics, and/or glass ceramics that include a predominant crystal phase including β-quartz solid solution, β-spodumene ss, cordierite, and lithium disilicate. The glass ceramic substrates may be strengthened using the chemical strengthening processes disclosed herein. In one or more embodiments, MAS-System glass ceramic substrates may be strengthened in Li₂SO₄ molten salt, whereby an exchange of 2Li⁺ for Mg²⁺ can occur.

The substrate 110 according to one or more embodiments can have a physical thickness ranging from about 100 μm to about 5 mm. Example substrate 110 physical thicknesses range from about 100 μm to about 500 μm (e.g., 100, 200, 300, 400 or 500 μm). Further example substrate 110 physical thicknesses range from about 500 μm to about 1000 μm (e.g., 500, 600, 700, 800, 900 or 1000 μm). The substrate 110 may have a physical thickness greater than about 1 mm (e.g., about 2, 3, 4, or 5 mm). In one or more specific embodiments, the substrate 110 may have a physical thickness of 2 mm or less or less than 1 mm. The substrate 110 may be acid polished or otherwise treated to remove or reduce the effect of surface flaws.

Optical Film

As shown in FIG. 5-6 , the optical film 120 may include a plurality of layers 130, 140, 150. Additional layers may also be included in optical film 120. Moreover, in some embodiments, one or more films or layers may be disposed on the opposite side of the substrate 110 from the optical film 120 (i.e., on major surface 114).

The physical thickness of the optical film 120 may be in the range from about 0.1 μm to about 3 μm. In some instances, the physical thickness of the optical film 120 may be in the range from about 0.1 μm to about 2.9 μm, from about 0.1 μm to about 2.8 μm, from about 0.1 μm to about 2.7 μm, from about 0.1 μm to about 2.6 μm, from about 0.1 μm to about 2.5 μm, from about 0.1 μm to about 2.4 μm, from about 0.1 μm to about 2.3 μm, from about 0.1 μm to about 2.2 μm, from about 0.1 μm to about 2.1 μm, from about 0.1 μm to about 2 μm, from about 0.5 μm to about 3 μm, from about 1 μm to about 3 μm, from about 1.1 μm to about 3 μm, from about 1.2 μm to about 3 μm, from about 1.3 μm to about 3 μm, from about 1.4 μm to about 3 μm, or from about 1.5 μm to about 3 μm, and all ranges and sub-ranges therebetween.

The optical film 120 may exhibit a maximum hardness of greater than about 5 GPa, as measured on the coated surface 101, by the Berkovich Indenter Hardness Test. For example, the optical film 120 may exhibit a hardness in the range from about 6 GPa to about 30 GPa, from about 7 GPa to about 30 GPa, from about 8 GPa to about 30 GPa, from about 9 GPa to about 30 GPa, from about 10 GPa to about 30 GPa, from about 12 GPa to about 30 GPa, from about 5 GPa to about 28 GPa, from about 5 GPa to about 26 GPa, from about 5 GPa to about 24 GPa, from about 5 GPa to about 22 GPa, from about 5 GPa to about 20 GPa, from about 12 GPa to about 25 GPa, from about 15 GPa to about 25 GPa, from about 16 GPa to about 24 GPa, from about 18 GPa to about 22 GPa and all ranges and sub-ranges therebetween. Such hardness values may be exhibited at indentation depths of about 50 nm or greater or about 100 nm or greater. In one or more embodiments, the indentation depths may be in the range from about 100 nm to about 300 nm, from about 100 nm to about 400 nm, from about 100 nm to about 500 nm, from about 100 nm to about 600 nm, from about 200 nm to about 300 nm, from about 200 nm to about 400 nm, from about 200 nm to about 500 nm, or from about 200 nm to about 600 nm.

In one or more embodiments, the optical film includes an optical interference layer 130 disposed on major surface 112 of the substrate 110, a scratch-resistant layer 140 disposed on the optical interference layer 130 and an optional capping layer 150 disposed on the scratch resistant layer 140. In the embodiment shown, the optical interference layer 130 is disposed between the substrate 110 and the scratch-resistant layer 140, thus modifying the interface between the substrate 110 and the scratch-resistant layer 140.

The optical film or any one or of the layers in the optical film may exhibit an extinction coefficient (at a wavelength of about 400 nm) of about 10-4 or less.

The optical interference layer 130 may include two or more sub-layers. In one or more embodiments, the two or more sub-layers may be characterized as having a different refractive index. Unless otherwise stated, refractive index values described herein are with reference a wavelength of about 550 nm. In embodiment, the optical interference layer 130 includes a first low RI sub-layer and a second high RI sub-layer. The difference in the refractive index of the first low RI sub-layer and the second high RI sub-layer may be about 0.01 or greater, 0.05 or greater, 0.1 or greater or even 0.2 or greater.

As shown in FIG. 6 , the optical interference layer may include a plurality of sub-layer sets (131). A single sub-layer set may include a first low RI sub-layer and a second high RI sub-layer. For example, sub-layer set 131 includes a first low RI sub-layer 131A and a second high RI sub-layer 131B. In some embodiments, the optical interference layer may include a plurality of sub-layer sets such that the first low RI sub-layer (designated for illustration as “L”) and the second high RI sub-layer (designated for illustration as “H”) may be provide the following sequence of sub-layers: L/H/L/H or H/L/H/L, such that the first low RI sub-layer and the second high RI sub-layer appear to alternate along the physical thickness of the optical interference layer. In the example in FIG. 6 , the optical interference layer 130 includes three sub-layer sets. In some embodiments, the optical interference layer 130 may include up to 10 sub-layer sets. For example, the optical interference layer 130 may include from about 2 to about 12 sub-layer sets, from about 3 to about 8 sub-layer sets, from about 3 to about 6 sub-layer sets.

In some embodiments, the optical interference layer may include one or more third sub-layers. The third sub-layer(s) may have a low RI, a high RI or a medium RI. In some embodiments, the third sub-layer(s) may have the same RI as the first low RI sub-layer 131A or the second high RI sub-layer 131B. In other embodiments, the third sub-layer(s) may have a medium RI that is between the RI of the first low RI sub-layer 131A and the RI of the second high RI sub-layer 131B. The third sub-layer(s) may be disposed between the plurality of sub-layer sets and the scratch-resistant layer 140 (see FIG. 12, 231C) or between the substrate and the plurality of sub-layer sets (see FIG. 12, 231D). Alternatively, the third sub-layer may be included in the plurality of sub-layer sets (not shown). The third sub-layer may be provided in the optical interference layer in the following exemplary configurations: L_(third sub-layer)/H/L/H/L; H_(third sub-layer)/L/H/L/H; L/H/L/H/L_(third sub-layer); H/L/H/L/H_(third sub-layer); L_(third sub-layer)/H/L/H/L/H_(third sub-layer); H_(third sub-layer)/L/H/L/H/L_(third sub-layer); L_(third sub-layer)/L/H/L/H; H_(third sub-layer)/H/L/H/L; H/L/H/L/L_(third sub-layer); L/H/L/H/H_(third sub-layer); L_(third sub-layer)/L/H/L/H/H_(third sub-layer); H_(third sub-layer)//H/L/H/L/L_(third sub-layer); L/M/H/L/M/H; H/M/L/H/M/L; M/L/H/L/M; and other combinations. In these configurations, “L” without any subscript refers to the first low RI sub-layer and “H” without any subscript refers to the second high RI sub-layer. Reference to “L_(third sub-layer)” refers to a third sub-layer having a low RI, “H_(third sub-layer)” refers to a third sub-layer having a high RI and “M” refers to a third sub-layer having a medium RI.

As used herein, the terms “low RI”, “high RI” and “medium RI” refer to the relative values for the RI to another (e.g., low RI<medium RI<high RI). In one or more embodiments, the term “low RI” when used with the first low RI sub-layer or with the third sub-layer, includes a range from about 1.3 to about 1.7 (e.g., about 1.4 to about 1.6, or about 1.46). In one or more embodiments, the term “high RI” when used with the second high RI sub-layer or with the third sub-layer, includes a range from about 1.6 to about 2.5 (e.g., about 1.8 to about 2.1, or about 1.9 to about 2.0). In some embodiments, the term “medium RI” when used with the third sub-layer, includes a range from about 1.55 to about 1.8. In some instances, the ranges for low RI, high RI and medium RI may overlap; however, in most instances, the sub-layers of the optical interference layer have the general relationship regarding RI of: low RI<medium RI<high RI.

Exemplary materials suitable for use in the optical interference layer 130 include: SiO₂, Al₂O₃, GeO₂, SiO, AlO_(x)N_(y), AlN, Si₃N₄, SiO_(x)N_(y), Si_(u)Al_(v)O_(x)N_(y), Ta₂O₅, Nb₂O₅, TiO₂, ZrO₂, TiN, MgO, MgF₂, BaF₂, CaF₂, SnO₂, HfO₂, Y₂O₃, MoO₃, DyF₃, YbF₃, YF₃, CeF₃, polymers, fluoropolymers, plasma-polymerized polymers, siloxane polymers, silsesquioxanes, polyimides, fluorinated polyimides, polyetherimide, polyethersulfone, polyphenylsulfone, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, acrylic polymers, urethane polymers, polymethylmethacrylate, other materials cited below as suitable for use in a scratch-resistant layer, and other materials known in the art. Some examples of suitable materials for use in the first low RI sub-layer include SiO₂, Al₂O₃, GeO₂, SiO, AlO_(x)N_(y), SiO_(x)N_(y), Si_(u)Al_(v)O_(x)N_(y), MgO, MgF₂, BaF₂, CaF₂, DyF₃, YbF₃, YF₃, and CeF₃. Some examples of suitable materials for use in the second high RI sub-layer include Si_(u)Al_(v)O_(x)N_(y), Ta₂O₅, Nb₂O₅, AlN, Si₃N₄, AlO_(x)N_(y), SiO_(x)N_(y), HfO₂, TiO₂, ZrO₂, Y₂O₃, Al₂O₃, and MoO₃.

In one or more embodiments at least one of the sub-layer(s) of the optical interference layer may include a specific optical thickness range. As used herein, the term “optical thickness” is determined by (n*d), where “n” refers to the RI of the sub-layer and “d” refers to the physical thickness of the sub-layer. In one or more embodiments, at least one of the sub-layers of the optical interference layer may include an optical thickness in the range from about 2 nm to about 200 nm, from about 10 nm to about 100 nm, or from about 15 nm to about 100 nm. In some embodiments, all of the sub-layers in the optical interference layer 130 may each have an optical thickness in the range from about 2 nm to about 200 nm, from about 10 nm to about 100 nm or from about 15 nm to about 100 nm. In some cases, at least one sub-layer of the optical interference layer 130 has an optical thickness of about 50 nm or greater. In some cases, each of the first low RI sub-layers have an optical thickness in the range from about 2 nm to about 200 nm, from about 10 nm to about 100 nm, or from about 15 nm to about 100 nm. In other cases, each of the second high RI sub-layers have an optical thickness in the range from about 2 nm to about 200 nm, from about 10 nm to about 100 nm, or from about 15 nm to about 100 nm. In yet other cases, each of the third sub-layers have an optical thickness in the range from about 2 nm to about 200 nm, from about 10 nm to about 100 nm, or from about 15 nm to about 100 nm.

In one or more embodiments, the optical interference layer 130 has a physical thickness of about 800 nm or less. The optical interference layer 130 may have a physical thickness in the range from about 10 nm to about 800 nm, from about 50 nm to about 800 nm, from about 100 nm to about 800 nm, from about 150 nm to about 800 nm, from about 200 nm to about 800 nm, from about 10 nm to about 750 nm, from about 10 nm to about 700 nm, from about 10 nm to about 650 nm, from about 10 nm to about 600 nm, from about 10 nm to about 550 nm, from about 10 nm to about 500 nm, from about 10 nm to about 450 nm, from about 10 nm to about 400 nm, from about 10 nm to about 350 nm, from about 10 nm to about 300 nm, from about 50 to about 300, from about 100 nm to about 200 nm, from about 125 nm to about 200 nm, from about 150 nm to about 190 nm, or from about 160 nm to about 180 nm, and all ranges and sub-ranges therebetween.

In some embodiments, the optical interference layer exhibits an average light reflectance of about 2% or less, 1.5% or less, 0.75% or less, 0.5% or less, 0.25% or less, 0.1% or less, or even 0.05% or less over the optical wavelength regime, when measured in an immersed state. As used herein, the phrase “immersed state” includes the measurement of the average reflectance by subtracting or otherwise removing reflections created by the article at interfaces other than those involving the optical interference layer. In some instances, the optical interference layer may exhibit such average light reflectance over other wavelength ranges such as from about 450 nm to about 650 nm, from about 420 nm to about 680 nm, from about 420 nm to about 740 nm, from about 420 nm to about 850 nm, or from about 420 nm to about 950 nm. In some embodiments, the optical interference layer exhibits an average light transmission of about 90% or greater, 92% or greater, 94% or greater, 96% or greater, or 98% or greater, over the optical wavelength regime.

The optical interference layer 130 of the embodiments described herein may be distinguished from layers that have a monotonic refractive index gradient. Articles that include the optical interference layer 130 between a scratch-resistant layer 140 and the substrate 110 exhibit improved optical performance (e.g., high average light transmission, low average light reflectance, low color shift as described herein), while reducing the physical thickness of the optical film 120. Monotonic refractive index gradient layers provide similar optical properties but may require greater physical thicknesses.

The scratch-resistant layer 140 of one or more embodiments may include an inorganic carbide, nitride, oxide, diamond-like material, or combination of these. Examples of suitable materials for the scratch-resistant layer 140 include metal oxides, metal nitrides, metal oxynitride, metal carbides, metal oxycarbides, and/or combinations thereof combination thereof. Exemplary metals include B, Al, Si, Ti, V, Cr, Y, Zr, Nb, Mo, Sn, Hf, Ta and W. Specific examples of materials that may be utilized in the scratch-resistant layer 140 may include Al₂O₃, AlN, AlO_(x)N_(y), Si₃N₄, SiO_(x)N_(y), Si_(u)Al_(v)O_(x)N_(y), diamond, diamond-like carbon, Si_(x)C_(y), Si_(x)O_(y)C_(z), ZrO₂, TiO_(x)N_(y) and combinations thereof.

The scratch resistant layer may also comprise nanocomposite materials, or materials with a controlled microstructure to improve hardness, toughness, or abrasion/wear resistance. For example the scratch resistant layer may comprise nanocrystallites in the size range from about 5 nm to about 30 nm. In embodiments, the scratch resistant layer may comprise transformation-toughened zirconia, partially stabilized zirconia, or zirconia-toughened alumina. In embodiments, the scratch-resistant layer exhibits a fracture toughness value greater than about 1 MPa √m and simultaneously exhibits a hardness value greater than about 8 GPa, as measured by the Berkovich Indenter Hardness Test.

The composition of the scratch-resistant layer 140 may be modified to provide specific properties (e.g., hardness, refractive index etc.). In one or more embodiments, the scratch resistant layer may include AlOxNy that includes up to about 60 atomic % aluminum, up to about 20 atomic % oxygen and up to about 40 atomic % nitrogen. In some embodiments, the AlOxNy material may include silicon. In some embodiments, the AlOxNy material may include aluminum in an amount in the range from about 45 atomic % to about 55 atomic % (e.g., about 50 atomic %), oxygen in an amount in the range from about 12 atomic % to about 20 atomic % (e.g., about 15 atomic % to about 17 atomic %), and nitrogen in an amount in the range from about 30 atomic % to about 35 atomic % (e.g., about 32 atomic % or about 33 atomic %).

In some instances the amount of oxygen in the scratch resistant layer may be controlled to form larger crystal sizes or smaller crystal sizes. In other words, the amount of oxygen may be modified to provide a desired crystallinity and/or crystal size (or size range) of the scratch resistant layer. The amount of nitrogen may be controlled to provide a desired hardness, as measured by the Berkovich Indenter Hardness Test. An increased amount of nitrogen relative to oxygen may provide a scratch resistant layer and thus an article including the same, which exhibits higher hardness than such a layer or article that includes less nitrogen relative to the amount of oxygen. Moreover, the amount of nitrogen to oxygen may alter the refractive index and thus may influence the transmittance and color shift of the article.

In one or more embodiments, the scratch-resistant layer 140 exhibits a hardness in the range from about 5 GPa to about 30 GPa as measured by the Berkovich Indenter Hardness Test (measured from the major surface of the scratch-resistant layer). In one or more embodiments, the scratch-resistant layer 140 exhibits a hardness in the range from about 6 GPa to about 30 GPa, from about 7 GPa to about 30 GPa, from about 8 GPa to about 30 GPa, from about 9 GPa to about 30 GPa, from about 10 GPa to about 30 GPa, from about 12 GPa to about 30 GPa, from about 5 GPa to about 28 GPa, from about 5 GPa to about 26 GPa, from about 5 GPa to about 24 GPa, from about 5 GPa to about 22 GPa, from about 5 GPa to about 20 GPa, from about 12 GPa to about 25 GPa, from about 15 GPa to about 25 GPa, from about 16 GPa to about 24 GPa, from about 18 GPa to about 22 GPa and all ranges and sub-ranges therebetween. In one or more embodiments, the scratch-resistant layer 140 may exhibit a hardness that is greater than 15 GPa, greater than 20 GPa, or greater than 25 GPa. In one or more embodiments, the scratch-resistant layer exhibits a hardness in the range from about 15 GPa to about 150 GPa, from about 15 GPa to about 100 GPa, or from about 18 GPa to about 100 GPa. These hardness values may be present at indentation depths of about 50 nm or greater, or about 100 nm or greater (e.g., in the range from about 100 nm to about 300 nm, from about 100 nm to about 400 nm, from about 100 nm to about 500 nm, from about 100 nm to about 600 nm, from about 200 nm to about 300 nm, from about 200 nm to about 400 nm, from about 200 nm to about 500 nm, or from about 200 nm to about 600 nm).

The physical thickness of the scratch-resistant layer 140 may be in the range from about 1.5 μm to about 3 μm. In some embodiments, the physical thickness of the scratch-resistant layer 140 may be in the range from about 1.5 μm to about 3 μm, from about 1.5 μm to about 2.8 μm, from about 1.5 μm to about 2.6 μm, from about 1.5 μm to about 2.4 μm, from about 1.5 μm to about 2.2 μm, from about 1.5 μm to about 2 μm, from about 1.6 μm to about 3 μm, from about 1.7 μm to about 3 μm, from about 1.8 μm to about 3 μm, from about 1.9 μm to about 3 μm, from about 2 μm to about 3 μm, from about 2.1 μm to about 3 μm, from about 2.2 μm to about 3 μm, from about 2.3 μm to about 3 μm, and all ranges and sub-ranges therebetween. In some embodiments, the physical thickness of the scratch-resistant layer 140 may be in the range from about 0.1 μm to about 2 μm, or from about 0.1 μm to about 1 μm, or from 0.2 μm to about 1 μm.

In one or more embodiments, the scratch-resistant layer 140 has a refractive index of about 1.6 or greater. In some instances, the refractive index of the scratch-resistant layer 140 may be about 1.65 or greater, 1.7 or greater, 1.8 or greater, 1.9 or greater, 2 or greater, or 2.1 or greater (e.g., in the range from about 1.8 to about 2.1, or from about 1.9 to about 2.0). The scratch-resistant layer may have a refractive index that is greater than the refractive index of the substrate 110. In specific embodiments, the scratch-resistant layer has a refractive index that is about 0.05 index units greater or about 0.2 index units greater than the refractive index of the substrate, when measured at a wavelength of about 550 nm.

The capping layer 150 of one or more embodiments may include a low refractive index material, such as SiO₂, Al₂O₃, GeO₂, SiO, AlO_(x)N_(y), SiO_(x)N_(y), Si_(u)Al_(v)O_(x)N_(y), MgO, MgF₂, BaF₂, CaF₂, DyF₃, YbF₃, YF₃, and CeF₃ and other such materials. The physical thickness of the capping layer may be in the range from about 0 to about 100 nm, from about 0.1 nm to about 50 nm, from about 1 nm to about 50 nm, from about 5 nm to about 50 nm, from about 10 nm to about 50 nm, from about 0 nm to about 40, from about 0 nm to about 30, from about 0 nm to about 20 nm, from about 0 nm to about 10 nm, from about 0.1 nm to about 15 nm, from about 0.1 nm to about 12 nm, from about 0.1 nm to about 10 nm, from about 0.1 nm to about 8 nm, from about 4 nm to about 30 nm, from about 4 nm to about 20 nm, from about 8 nm to about 12 nm, from about 9 nm to about 10 nm, and all ranges and sub-ranges therebetween. The refractive index of the capping layer may be in the range from about 1.4 to about 1.6 (e.g., about 1.46). The capping layer may exhibit an intrinsic hardness in the range from about 7 GPa to about 10 GPa, as measured by the Berkovich Indenter Hardness Test (as measured on the surface of a layer of the same material of the capping layer, formed in the same manner, but having a thickness of about 1 micrometer or greater).

In one or more embodiments, the article has a refractive index of about 1.7 or greater at the coated surface 101, which may include the capping layer. The capping layer 150 may formed using silane-based low-friction materials, including fluorosilane, alkyl silane, silsesquioxane, and the like, either by liquid deposition or vapor deposition methods. In one or more embodiments, the capping layer may comprise two or more materials or two or more sub-layers (e.g., 4 sub-layers or 6 sub-layers). The capping layer may provide an anti-reflective function especially where multiple sub-layers are utilized. The sub-layers may include different refractive indices and may include layers with high refractive indices (H) and low refractive indices (L) where “high” and “low” are with respect to one another and within known ranges for anti-reflective films. The sub-layers may be arranged so that high and low refractive index sub-layers alternate. The materials or sub-layers can include, for example SiO₂ or SiO_(x)N_(y). In such embodiments, the one or more sub-layers can have a thickness each or combined in the range from about 4 nm to about 50 nm. In some embodiments, the capping layer 150 may include a silane-based low-friction sub-layer having a thickness in the range from about 0.1 nm to about 20 nm, disposed on underlying sub-layers of the capping layer (e.g., the SiO₂ and/or SiO_(x)N_(y) layer(s)).

In some embodiments, the optical interference layer 130 may also comprise a crack mitigating layer. This crack mitigating layer may suppress or prevent crack bridging between the scratch resistant layer 140 and the substrate 110, thus modifying or improving the mechanical properties or strength of the article. Embodiments of crack mitigating layers are further described in U.S. patent application Ser. Nos. 14/052,055, 14/053,093 and 14/053,139, which are incorporated herein by reference. The crack mitigating layer may comprise crack blunting materials, crack deflecting materials, crack arresting materials, tough materials, or controlled-adhesion interfaces. The crack mitigating layer may comprise polymeric materials, nanoporous materials, metal oxides, metal fluorides, metallic materials, or other materials mentioned herein for use in either the optical interference layer 130 or the scratch resistant layer 140. The structure of the crack mitigating layer may be a multilayer structure, wherein the multilayer structure is designed to deflect, suppress, or prevent crack propagation while simultaneously providing the optical interference benefits described herein. The crack mitigating layer may include nanocrystallites, nanocomposite materials, transformation toughened materials, multiple layers of organic material, multiple layers of inorganic material, multiple layers of interdigitating organic and inorganic materials, or hybrid organic-inorganic materials. The crack mitigating layer may have a strain to failure that is greater than about 2%, or greater than about 10%. These crack mitigating layers can also be combined separately with the substrate, scratch resistant layer, and optical interference layer(s) described herein; it is not strictly required that the crack mitigating layer is simultaneously acting as an optical interference layer. In embodiments, the crack mitigating layer can perform its function in the presence or in the absence of an optical interference layer (and vice versa). The design of the optical interference layer can be adjusted, if needed, to accommodate the presence of a crack mitigating layer.

The crack mitigating layer may include tough or nanostructured inorganics, for example, zinc oxide, certain Al alloys, Cu alloys, steels, or stabilized tetragonal zirconia (including transformation toughened, partially stabilized, yttria stabilized, ceria stabilized, calcia stabilized, and magnesia stabilized zirconia); zirconia-toughened ceramics (including zirconia toughened alumina); ceramic-ceramic composites; carbon-ceramic composites; fiber- or whisker-reinforced ceramics or glass-ceramics (for example, SiC or Si₃N₄ fiber- or whisker-reinforced ceramics); metal-ceramic composites; porous or non-porous hybrid organic-inorganic materials, for example, nanocomposites, polymer-ceramic composites, polymer-glass composites, fiber-reinforced polymers, carbon-nanotube- or graphene-ceramic composites, silsesquioxanes, polysilsesquioxanes, or “ORMOSILs” (organically modified silica or silicate), and/or a variety of porous or non-porous polymeric materials, for example siloxanes, polysiloxanes, polyacrylates, polyacrylics, PI (polyimides), fluorinated polyimide, polyamides, PAI (polyamideimides), polycarbonates, polysulfones, PSU or PPSU (polyarylsulfones), fluoropolymers, fluoroelastomers, lactams, polycylic olefins, and similar materials, including, but not limited to PDMS (polydimethylsiloxane), PMMA (poly(methyl methacrylate)), BCB (benzocyclobutene), PEI (polyethyletherimide), poly(arylene ethers) such as PEEK (poly-ether-ether-ketone), PES (polyethersulfone) and PAR (polyarylate), PET (polyethylene terephthalate), PEN (polyethylene napthalate=poly(ethylene-2,6-napthalene dicarboxylate), FEP (fluorinated ethylene propylene), PTFE (polytetrafluoroethylene), PFA (perfluroalkoxy polymer, e.g., trade names Teflon®, Neoflon®) and similar materials. Other suitable materials include modified polycarbonates, some versions of epoxies, cyanate esters, PPS (polyphenylsulfides), polyphenylenes, polypyrrolones, polyquinoxalines, and bismaleimides.

The physical and/or optical thicknesses of the layers of the optical film 120 can be adjusted to achieve desired optical and mechanical properties (e.g., hardness). For example, the scratch-resistant layer 140 may be can be made thinner, for example in the range from about 100 nm to about 500 nm, while still providing some resistance to scratch, abrasion, or damage events (including drop events of the article onto hard surfaces such as asphalt, cement, or sandpaper). The capping layer physical and/or optical thickness can also be adjusted. The capping layer may be included when even lower total reflection is desired. The capping layer may also be included to further tune color of the article. For example, the optical films described herein minimize color shift with changing incidence illumination angle in a* or b* coordinates, but may also exhibit a slight slope to the reflectance spectra. A capping layer 150 may be included in the optical film 120 and the physical and/or optical thickness of the capping layer may be adjusted slightly (e.g., from about 10 nm to about 14 nm) to provide an even flatter reflectance spectrum (or a reflectance spectrum with oscillations having even smaller amplitudes) across the optical wavelength regime.

The optical film 120 may be formed using various deposition methods such as vacuum deposition techniques, for example, chemical vapor deposition (e.g., plasma enhanced chemical vapor deposition, low-pressure chemical vapor deposition, atmospheric pressure chemical vapor deposition, and plasma-enhanced atmospheric pressure chemical vapor deposition), physical vapor deposition (e.g., reactive or nonreactive sputtering or laser ablation), thermal or e-beam evaporation and/or atomic layer deposition. One or more layers of the optical film 120 may include nano-pores or mixed-materials to provide specific refractive index ranges or values.

The physical thicknesses of the layers or sub-layers of the optical film 120 may vary by less than about 10 nm, less than about 5 nm, less than about 1 nm or less than about 0.5 nm (representing the range of six standard deviations from the target value) to achieve the maximum targeted repeatability (e.g., a* and b* variations no greater than +/−0.2 for reflected F2 illumination). In some embodiments, larger variations in physical thicknesses of the layers can be tolerated while still achieving the desired targets of the invention for some applications (e.g., a* and b* variations no greater than +/−2.0 for reflected F2 illumination).

High-angle optical performance may be improved in some embodiments by adding additional layers to the optical film 120 and/or the article 100. In some cases, these additional layers can extend the wavelengths at which the reflectance spectrum has low amplitude oscillations (e.g., into the near-IR wavelengths, such as to 800 nm, 900 nm, or even 1000 nm). This leads to lower oscillations and lower color at high incidence angles, because generally the entire reflectance spectra of the article shifts to shorter wavelengths at higher light incidence angles. In some cases, this extended-band performance can be achieved by adjusting the interference layer design, for example by allowing a higher oscillation amplitude to achieve a wider-wavelength-band of low oscillations, without necessarily adding more layers. This extended-band or wide-wavelength-band of low oscillations (correlated to an extended band of low reflectance for the interference layers) can also be useful in making the article tolerant to deposition non-uniformity, substrate curvature, substrate sculpting, or substrate shaping which causes shadowing during directional deposition processes, or other geometry factors that cause a substantially uniform relative shift in all layer thicknesses relative to the typically ideal target thicknesses.

The optical film of one or more embodiments may include or exhibit a sensing function or include or exhibit one or more properties enabling sensing. As used herein, sensing may include optical sensing, electrical sensing, magnetic sensing, mechanical sensing or a combination thereof. The sensing function may include capacitive sensing, resistive sensing, inductive sensing, surface acoustic wave sensing, photoelectric sensing, or other known sensing functions. In one or more embodiments, a portion of the optical film (e.g., a single or select layer(s)) may exhibit such sensing function or one or more properties enabling sensing. In one embodiment, the optical film or portion thereof may exhibit piezoelectric properties, pyro-electric properties or a combination thereof. In some embodiments, the optical film may exhibit piezoelectric properties but be essentially free of pyro-electric properties and vice versa. One or more piezoelectric layers within the optical film may comprise crystalline or polycrystalline material, and may also exhibit the hardness described herein and/or a low optical absorption (and/or high optical transparency). In some embodiments, the piezoelectric properties may be present in one or more aluminum nitride or oxygen-doped aluminum nitride layers within the optical film. In some embodiments, such optical films may sense a magnitude of force or pressure, sense acoustic signals, and/or sense acceleration. Such embodiments may be described as having an optical film including a sensor or sensor layer. The optical film may include or may be used with one or more electrically conducting layers, transparent conductor layers (i.e. optically transparent and electrically conducting layers) and/or optical waveguiding layers to perform such sensing functions. The optical film may be coupled to a signal detector, electrode, or signal processor in order to capture, store, or interpret the output of the sensing function.

The articles disclosed herein may include articles with a display (or display articles) (e.g., consumer electronics, including mobile phones, tablets, computers, navigation systems, and the like), architectural articles, transportation articles (e.g., automotive, trains, aircraft, sea craft, etc.), appliance articles, or any article that requires some transparency, scratch-resistance, abrasion resistance or a combination thereof.

EXAMPLES

Various embodiments will be further clarified by the following examples. Examples 1-9 used modeling to understand the reflectance spectra and color shift of articles that included an optical film with an optical interference layer, a scratch-resistant layer and a capping layer. The modeling was based on collected refractive index data from formed layers of various materials and a strengthened aluminoborosilicate (“ABS”) glass substrate. Examples 10, 11, and Comparative Example 12 are experimentally fabricated multilayer working examples which further demonstrate the principles of modeling Examples 1-9.

The layers were formed by DC reactive sputtering, reactive DC and radio frequency (RF) sputtering, and e-beam evaporation onto silicon wafers. Some of the formed layers included SiO₂, Nb₂O₅, or Al₂O₃ and were deposited onto silicon wafers by DC reactive sputtering from a silicon, niobium or aluminum target (respectively) at a temperature of about 50° C. using ion assist. Layers formed in this manner are designated with the indicator “RS”. Other layers including SiO₂ were deposited onto silicon wafers by e-beam evaporation by heating the wafer to 300° C. and without ion assist. Such layers are designated with the indicator “E”. Layers of Ta₂O₅ were deposited onto silicon wafers by e-beam evaporation by heating the wafer to 300° C. and without ion assist.

Layers of Si_(u)Al_(v)O_(x)N_(y) were deposited onto silicon wafers by DC reactive sputtering combined with RF superimposed DC sputtering, with ion assist using a sputter deposition tool supplied by AJA-Industries. The wafer was heated to 200° C. during deposition and silicon targets having a 3 inch diameter and an aluminum targets having a 3 inch diameter were used. Reactive gases used included nitrogen and oxygen and argon was used as the inert gas. The RF power was supplied to the silicon target at 13.56 Mhz and DC power was supplied to the aluminum target. The resulting Si_(u)Al_(v)O_(x)N_(y) layers had a refractive index at 550 nm of about 1.95 and a measured hardness of greater than about 15 GPa, using a Berkovich indenter on the surface of the Si_(u)Al_(v)O_(x)N_(y) layer being tested, as described herein.

The refractive indices (as a function of wavelength) of the formed layers of the optical film and the glass substrates were measured using spectroscopic ellipsometry. Tables 1-7 include the refractive indices and dispersion curves measured. The refractive indices thus measured were then used to calculate reflectance spectra and angular color shift for the various modeled Examples.

TABLE 1 Refractive indices and dispersion curve for a RS-SiO2 layer vs. wavelength. Material SiO2-RS Wavelength Refractive Extinction (nm) Index (n) Coefficient (k) 246.5 1.52857 0.0 275.2 1.51357 0.0 300.8 1.50335 0.0 324.7 1.49571 0.0 350.2 1.48911 0.0 375.8 1.48374 0.0 399.7 1.47956 0.0 425.2 1.47583 0.0 450.7 1.47269 0.0 476.3 1.47002 0.0 500.2 1.46788 0.0 525.7 1.46589 0.0 549.5 1.46427 0.0 575.0 1.46276 0.0 600.5 1.46143 0.0 625.9 1.46026 0.0 649.7 1.45928 0.0 675.1 1.45835 0.0 700.5 1.45751 0.0 725.9 1.45676 0.0 751.3 1.45609 0.0 775.0 1.45551 0.0 800.4 1.45496 0.0 850.9 1.45399 0.0 899.8 1.45320 0.0 950.2 1.45252 0.0 999.0 1.45195 0.0 1100.0 1.45100 0.0 1199.6 1.45028 0.0 1302.0 1.44971 0.0 1400.8 1.44928 0.0 1499.7 1.44892 0.0 1599.0 1.44863 0.0 1688.4 1.44841 0.0

TABLE 2 Refractive indices and dispersion curve for a Si_(u)Al_(v)O_(x)N_(y) layer vs. wavelength. Material SiAlON-195 Wavelength Refractive Extinction (nm) Index (n) Coefficient (k) 206.6 2.37659 0.21495 225.4 2.28524 0.11270 251.0 2.18818 0.04322 275.5 2.12017 0.01310 300.9 2.06916 0.00128 324.6 2.03698 0.0 350.2 2.01423 0.0 360.4 2.00718 0.0 371.2 2.00059 0.0 380.3 1.99562 0.0 389.9 1.99090 0.0 400.0 1.98640 0.0 410.5 1.98213 0.0 421.7 1.97806 0.0 430.5 1.97513 0.0 439.7 1.97230 0.0 449.2 1.96958 0.0 459.2 1.96695 0.0 469.6 1.96441 0.0 480.6 1.96197 0.0 492.0 1.95961 0.0 499.9 1.95808 0.0 512.3 1.95586 0.0 520.9 1.95442 0.0 529.9 1.95301 0.0 539.1 1.95165 0.0 548.6 1.95031 0.0 558.5 1.94900 0.0 568.7 1.94773 0.0 579.4 1.94649 0.0 590.4 1.94528 0.0 601.9 1.94410 0.0 613.8 1.94295 0.0 619.9 1.94239 0.0 632.6 1.94128 0.0 639.1 1.94074 0.0 652.6 1.93968 0.0 666.6 1.93864 0.0 681.2 1.93763 0.0 696.5 1.93665 0.0 712.6 1.93569 0.0 729.3 1.93477 0.0 746.9 1.93386 0.0 765.3 1.93299 0.0 784.7 1.93214 0.0 805.1 1.93131 0.0 826.6 1.93051 0.0 849.2 1.92973 0.0 873.1 1.92898 0.0 898.4 1.92825 0.0 925.3 1.92754 0.0 953.7 1.92686 0.0 999.9 1.92587 0.0 1050.7 1.92494 0.0 1107.0 1.92406 0.0 1169.7 1.92323 0.0 1239.8 1.92245 0.0 1319.0 1.92172 0.0 1408.9 1.92103 0.0 1512.0 1.92040 0.0 1631.4 1.91981 0.0 1771.2 1.91926 0.0 1999.8 1.91861 0.0

TABLE 3 Refractive indices and dispersion curve for a strengthened aluminoborosilicate glass substrate vs. wavelength. Material ABS glass Wavelength Refractive Extinction (nm) Index (n) Coefficient (k) 350.6 1.53119 0.0 360.7 1.52834 0.0 370.8 1.52633 0.0 380.8 1.52438 0.0 390.9 1.52267 0.0 400.9 1.52135 0.0 411.0 1.52034 0.0 421.0 1.51910 0.0 431.1 1.51781 0.0 441.1 1.51686 0.0 451.2 1.51600 0.0 461.2 1.51515 0.0 471.2 1.51431 0.0 481.3 1.51380 0.0 491.3 1.51327 0.0 501.3 1.51259 0.0 511.4 1.51175 0.0 521.4 1.51124 0.0 531.4 1.51082 0.0 541.5 1.51040 0.0 551.5 1.50999 0.0 561.5 1.50959 0.0 571.5 1.50918 0.0 581.6 1.50876 0.0 591.6 1.50844 0.0 601.6 1.50828 0.0 611.6 1.50789 0.0 621.7 1.50747 0.0 631.7 1.50707 0.0 641.7 1.50667 0.0 651.7 1.50629 0.0 661.7 1.50591 0.0 671.8 1.50555 0.0 681.8 1.50519 0.0 691.8 1.50482 0.0 701.8 1.50445 0.0 709.8 1.50449 0.0 719.8 1.50456 0.0 729.9 1.50470 0.0 739.9 1.50484 0.0 749.9 1.50491 0.0

TABLE 4 Refractive indices and dispersion curve for a RS-Al₂O₃ layer vs. wavelength. Material Al2O3-RS Wavelength Refractive Extinction (nm) Index (n) Coefficient (k) 251.3 1.76256 0.0 275.2 1.74075 0.0 300.8 1.72358 0.0 324.7 1.71136 0.0 350.2 1.70121 0.0 375.8 1.69321 0.0 401.3 1.68679 0.0 425.2 1.68185 0.0 450.7 1.67747 0.0 474.7 1.67402 0.0 500.2 1.67089 0.0 525.7 1.66823 0.0 549.5 1.66608 0.0 575.0 1.66408 0.0 600.5 1.66234 0.0 625.9 1.66082 0.0 649.7 1.65955 0.0 675.1 1.65835 0.0 700.5 1.65728 0.0 725.9 1.65633 0.0 749.7 1.65552 0.0 775.0 1.65474 0.0 800.4 1.65404 0.0 850.9 1.65282 0.0 899.8 1.65184 0.0 950.2 1.65098 0.0 999.0 1.65027 0.0 1100.0 1.64909 0.0 1199.6 1.64821 0.0 1302.0 1.64751 0.0 1400.8 1.64698 0.0 1499.7 1.64654 0.0 1599.0 1.64619 0.0 1688.4 1.64592 0.0

TABLE 5 Refractive indices and dispersion curve for an E-Ta₂O₅ layer vs. wavelength. Material Ta2O5-E Wavelength Refractive Extinction (nm) Index (n) Coefficient (k) 299.5 2.31978 0.01588 310.0 2.27183 0.00049 319.5 2.23697 0.0 329.7 2.20688 0.0 340.6 2.18080 0.0 350.2 2.16164 0.0 360.4 2.14448 0.0 369.0 2.13201 0.0 380.3 2.11780 0.0 389.9 2.10741 0.0 399.9 2.09780 0.0 410.5 2.08888 0.0 421.7 2.08059 0.0 430.5 2.07475 0.0 439.7 2.06920 0.0 449.2 2.06394 0.0 459.2 2.05892 0.0 469.6 2.05415 0.0 480.6 2.04960 0.0 488.1 2.04669 0.0 499.9 2.04248 0.0 512.3 2.03846 0.0 520.9 2.03588 0.0 529.8 2.03337 0.0 539.1 2.03094 0.0 548.6 2.02857 0.0 558.5 2.02627 0.0 568.7 2.02403 0.0 579.4 2.02186 0.0 590.4 2.01974 0.0 601.9 2.01768 0.0 613.8 2.01567 0.0 619.9 2.01469 0.0 632.6 2.01276 0.0 645.8 2.01088 0.0 659.5 2.00905 0.0 673.8 2.00726 0.0 688.8 2.00552 0.0 704.5 2.00382 0.0 729.3 2.00135 0.0 746.9 1.99975 0.0 774.9 1.99743 0.0 805.1 1.99518 0.0 826.6 1.99372 0.0 849.2 1.99230 0.0 898.4 1.98955 0.0 953.7 1.98692 0.0 999.9 1.98502 0.0 1050.7 1.98318 0.0 1107.0 1.98140 0.0 1148.0 1.98024 0.0 1192.2 1.97910 0.0 1239.8 1.97799 0.0 1291.5 1.97690 0.0 1347.7 1.97584 0.0 1408.9 1.97479 0.0 1476.0 1.97376 0.0 1549.8 1.97276 0.0

TABLE 6 Refractive indices and dispersion curve for an E-SiO₂ layer vs. wavelength. Material SiO2-E Wavelength Refractive Extinction (nm) Index (n) Coefficient (k) 299.5 1.48123 0.00296 310.0 1.47856 0.00283 319.5 1.47636 0.00273 329.7 1.47424 0.00262 340.6 1.47221 0.00252 350.2 1.47057 0.00244 360.4 1.46899 0.00236 369.0 1.46776 0.00229 380.3 1.46628 0.00221 389.9 1.46513 0.00215 399.9 1.46401 0.00209 410.5 1.46292 0.00203 421.7 1.46187 0.00197 430.5 1.46110 0.00192 439.7 1.46035 0.00188 449.2 1.45961 0.00183 459.2 1.45890 0.00179 469.6 1.45820 0.00174 480.6 1.45752 0.00170 488.1 1.45708 0.00167 499.9 1.45642 0.00163 512.3 1.45579 0.00158 520.9 1.45537 0.00156 529.8 1.45497 0.00153 539.1 1.45457 0.00150 548.6 1.45418 0.00147 558.5 1.45379 0.00144 568.7 1.45341 0.00142 579.4 1.45304 0.00139 590.4 1.45268 0.00136 601.9 1.45233 0.00133 613.8 1.45198 0.00131 619.9 1.45181 0.00129 632.6 1.45147 0.00126 639.1 1.45130 0.00125 652.5 1.45098 0.00122 659.5 1.45082 0.00121 673.8 1.45050 0.00118 681.2 1.45035 0.00117 688.8 1.45019 0.00116 704.5 1.44989 0.00113 720.8 1.44960 0.00110 746.9 1.44917 0.00106 774.9 1.44876 0.00102 805.1 1.44836 0.00098 826.6 1.44811 0.00096 849.2 1.44786 0.00093 898.4 1.44738 0.00088 953.7 1.44693 0.00083 999.9 1.44661 0.00079 1050.7 1.44631 0.00075 1107.0 1.44602 0.00071 1148.0 1.44584 0.00068 1192.2 1.44566 0.00066 1239.8 1.44549 0.00063 1291.5 1.44533 0.00061 1347.7 1.44517 0.00058 1408.9 1.44502 0.00056 1476.0 1.44488 0.00053 1549.8 1.44474 0.00050

TABLE 7 Refractive indices and dispersion curve for an RS-Nb₂O₅ layer vs. wavelength. Material Nb2O5-RS Wavelength Refractive Extinction (nm) Index (n) Coefficient (k) 206.6 2.04389 0.66079 250.0 2.32991 1.05691 300.2 3.14998 0.45732 325.0 2.94490 0.12012 350.2 2.74715 0.02027 375.1 2.62064 0.00048 400.6 2.53696 0.0 425.3 2.48169 0.0 450.0 2.44210 0.0 475.0 2.41223 0.0 500.9 2.38851 0.0 525.4 2.37086 0.0 549.8 2.35647 0.0 575.3 2.34409 0.0 600.4 2.33392 0.0 624.6 2.32557 0.0 650.8 2.31779 0.0 675.7 2.31142 0.0 700.5 2.30583 0.0 725.1 2.30093 0.0 749.1 2.29665 0.0 774.9 2.29255 0.0 799.9 2.28898 0.0 849.2 2.28288 0.0 901.7 2.27749 0.0 999.9 2.26958 0.0 1102.1 2.26342 0.0 1203.7 2.25867 0.0 1298.3 2.25513 0.0 1400.9 2.25198 0.0 1502.8 2.24939 0.0 1599.8 2.24730 0.0 1698.4 2.24547 0.0 1796.9 2.24389 0.0 1892.9 2.24254 0.0 1999.7 2.24122 0.0 2066.4 2.24047 0.0

Example 1

Modeled Example 1 included an article having the same structure as shown in FIG. 6 . Modeled Example 1 included a chemically strengthened alkali aluminoborosilicate glass substrate and an optical film disposed on the substrate. The optical film included an optical interference layer with three sets of sub-layers, a scratch-resistant layer disposed on the optical interference layer and a capping layer disposed on the scratch-resistant layer. The optical film materials and thicknesses of each layer, in the order arranged in the optical film, are provided in Table 8.

TABLE 8 Optical film attributes for modeled Example 1. Modeled Physical Layer Material Thickness Ambient medium Air Immersed Capping layer RS-SiO₂  9.5 nm Scratch-resistant layer Si_(u)Al_(v)O_(x)N_(y)  2000 nm Optical 1^(st) low RI sub-layer RS-SiO₂  8.22 nm interference 2^(nd) high RI sub-layer Si_(u)Al_(v)O_(x)N_(y) 46.39 nm layer 1^(st) low RI sub-layer RS-SiO₂   29 nm 2^(nd) high RI sub-layer Si_(u)Al_(v)O_(x)N_(y) 27.87 nm 1^(st) low RI sub-layer RS-SiO₂ 49.63 nm 2^(nd) high RI sub-layer Si_(u)Al_(v)O_(x)N_(y)  9.34 nm Substrate ABS Glass Immersed

The calculated reflectance spectrum for modeled Example 1 is shown in FIG. 7 . As shown in FIG. 7 , the oscillations in the reflectance spectrum are small (i.e., less than about 0.5 percentage points over the optical wavelength regime), leading to relatively low calculated visible color shift for a 10 degree observer, over a range of incidence viewing angles from 60 degrees to normal incidence, under an F2 illuminant, as shown in FIG. 8 . FIG. 7 shows a target having a radius of 0.2, centered on the color coordinates of the substrate without the optical film disposed thereon, under F2 illumination.

Example 2

Modeled Example 2 included an article 200 with a chemically strengthened alkali aluminoborosilicate substrate 210 and an optical film 220 disposed on the substrate. The optical film 220 included an optical interference layer 230, a scratch-resistant layer 240 disposed on the optical interference layer, and a capping layer 250, as shown in FIG. 9 . The optical interference layer 230 included four sets of sub-layers 231A, 231B. The optical film materials and thicknesses of each layer, in the order arranged in the optical film, are provided in Table 9.

TABLE 9 Optical film attributes for modeled Example 2. Layer Material Modeled Thickness Ambient medium Air Immersed Capping layer RS-SiO₂  9.5 nm Scratch-resistant layer Si_(u)Al_(v)O_(x)N_(y)  2000 nm Optical 1^(st) low RI sub-layer RS-SiO₂  4.83 nm interference 2^(nd) high RI sub-layer Si_(u)Al_(v)O_(x)N_(y) 53.16 nm layer 1^(st) low RI sub-layer RS-SiO₂ 19.63 nm 2^(nd) high RI sub-layer Si_(u)Al_(v)O_(x)N_(y) 38.29 nm 1^(st) low RI sub-layer RS-SiO₂ 40.97 nm 2^(nd) high RI sub-layer Si_(u)Al_(v)O_(x)N_(y) 21.73 nm 1^(st) low RI sub-layer RS-SiO₂ 54.88 nm 2^(nd) high RI sub-layer Si_(u)Al_(v)O_(x)N_(y)  7.05 nm Substrate ABS Glass Immersed

The calculated reflectance spectrum for the modeled Example 2 is shown in FIG. 10 . As shown in FIG. 10 , the oscillations in the reflectance spectrum are small (i.e., less than about 0.5 percentage points over the optical wavelength regime), leading to relatively low calculated visible color shift fora 10 degree observer, over a range of incidence viewing angles from 60 degrees to normal incidence, under an F2 illuminant, as shown in FIG. 11 . FIG. 11 shows a target having a radius of 0.2, centered on the color coordinates of the substrate without the optical film disposed thereon, under F2 illumination.

Example 3

Modeled Example 3 included an article 300 with a chemically strengthened alkali aluminoborosilicate substrate 310 and an optical film 320 disposed on the substrate. The optical film 320 included an optical interference layer 330, a scratch resistant layer 340 disposed on the optical interference layer, and a capping layer 350 disposed on the scratch-resistant layer 250. The optical interference layer included two sets of sub-layers 331A, 331B, a third sub-layer 331C disposed between the plurality of sub-layers and the scratch-resistant layer, and a third sub-layer 331D disposed between the plurality of sub-layers and the substrate, as shown in FIG. 12 . The optical film materials and thicknesses of each layer, in the order arranged in the optical film, are provided in Table 10.

TABLE 10 Optical film attributes for modeled Example 3. Layer Material Modeled Thickness Ambient medium Air Immersed Capping layer RS-SiO₂  9.5 nm Scratch-resistant layer Si_(u)Al_(v)O_(x)N_(y)  2000 nm Optical Third sub-layer RS-Al₂O₃  13.5 nm interference 2^(nd) high RI sub-layer Si_(u)Al_(v)O_(x)N_(y) 43.58 nm layer 1^(st) low RI sub-layer RS-SiO₂ 28.85 nm 2^(nd) high RI sub-layer Si_(u)Al_(v)O_(x)N_(y) 27.48 nm 1^(st) low RI sub-layer RS-SiO₂ 40.62 nm Third sub-layer RS-Al₂O₃ 27.26 nm Substrate ABS Glass Immersed

The calculated reflectance spectrum for the modeled Example 3 is shown in FIG. 13 . As shown in FIG. 13 , the oscillations in the reflectance spectrum are small (i.e., less than about 0.5 percentage points over the optical wavelength regime), leading to relatively low calculated visible color shift for a 10 degree observer, over a range of incidence viewing angles from 60 degrees to normal incidence, under an F2 illuminant, as shown in FIG. 14 . FIG. 14 shows a target having a radius of 0.2, centered on the color coordinates of the substrate without the optical film disposed thereon, under F2 illumination.

Example 4

Modeled Example 4 included an article 400 with a chemically strengthened alkali aluminoborosilicate substrate 410 and an optical film 420 disposed on the substrate. The optical film 420 included an optical interference layer 430, a scratch resistant layer 440 disposed on the optical interference layer, and a capping layer 450 disposed on the scratch-resistant layer. The optical interference layer included three sets of sub-layers 431A, 431B, a third sub-layer 431C disposed between the plurality of sub-layers and the scratch-resistant layer, and a third sub-layer 431D disposed between the plurality of sub-layers and the substrate, as shown in FIG. 15 . The optical film materials and thicknesses of each layer, in the order arranged in the optical film, are provided in Table 11.

TABLE 11 Optical film attributes for modeled Example 4. Layer Material Modeled Thickness Ambient medium Air Immersed Capping layer RS-SiO₂  9.5 nm Scratch-resistant layer Si_(u)Al_(v)O_(x)N_(y)  2000 nm Optical Third sub-layer RS-Al₂O₃ 10.20 nm interference 2^(nd) high RI sub-layer Si_(u)Al_(v)O_(x)N_(y) 49.01 nm layer 1^(st) low RI sub-layer RS-SiO₂ 23.30 nm 2^(nd) high RI sub-layer Si_(u)Al_(v)O_(x)N_(y) 35.04 nm 1^(st) low RI sub-layer RS-SiO₂ 44.95 nm 2^(nd) high RI sub-layer Si_(u)Al_(v)O_(x)N_(y) 19.02 nm 1^(st) low RI sub-layer RS-SiO₂ 50.45 nm Third sub-layer RS-Al₂O₃ 17.16 nm Substrate ABS Glass Immersed

The calculated reflectance spectrum for the modeled Example 4 is shown in FIG. 16 . As shown in FIG. 16 , the oscillations in the reflectance spectrum are small (i.e., less than about 0.5 percentage points over the optical wavelength regime), leading to relatively low calculated visible color shift for a 10 degree of server, over a range of incidence viewing angles from 60 degrees to normal incidence, under an F2 illuminant, as shown in FIG. 17 . FIG. 17 shows a target having a radius of 0.2, centered on the color coordinates of the substrate without the optical film disposed thereon, under F2 illumination.

Example 5

Modeled Example 5 included an article 500 with a chemically strengthened alkali aluminoborosilicate substrate 510 and an optical film 520 disposed on the substrate. The optical film 520 included an optical interference layer 530, a scratch resistant layer 540 disposed on the optical interference layer, and a capping layer 550 disposed on the scratch-resistant layer 550. The optical interference layer included six sets of sub-layers 531A, 531B and a third sub-layer 531C disposed between the plurality of sub-layers and the scratch-resistant layer, as shown in FIG. 18 . The optical film materials and thicknesses of each layer, in the order arranged in the optical film, are provided in Table 12.

TABLE 12 Optical film attributes for modeled Example 5. Layer Material Modeled Thickness Ambient medium Air Immersed Capping layer RS-SiO₂   14 nm Scratch-resistant layer Si_(u)Al_(v)O_(x)N_(y)  2000 nm Optical Third sub-layer RS-Al₂O₃  7.05 nm interference 2^(nd) high RI sub-layer Si_(u)Al_(v)O_(x)N_(y) 54.65 nm layer 1^(st) low RI sub-layer RS-Al₂O₃ 24.59 nm 2^(nd) high RI sub-layer Si_(u)Al_(v)O_(x)N_(y) 37.96 nm 1^(st) low RI sub-layer RS-Al₂O₃ 52.53 nm 2^(nd) high RI sub-layer Si_(u)Al_(v)O_(x)N_(y) 17.48 nm 1^(st) low RI sub-layer RS-Al₂O₃ 90.07 nm 2^(nd) high RI sub-layer Si_(u)Al_(v)O_(x)N_(y) 20.63 nm 1^(st) low RI sub-layer RS-Al₂O₃ 38.15 nm 2^(nd) high RI sub-layer Si_(u)Al_(v)O_(x)N_(y) 84.11 nm 1^(st) low RI sub-layer RS-Al₂O₃  6.87 nm 2^(nd) high RI sub-layer Si_(u)Al_(v)O_(x)N_(y) 48.85 nm 1^(st) low RI sub-layer RS-Al₂O₃ 81.63 nm Substrate ABS Glass Immersed

The calculated reflectance spectrum for the modeled Example 5 is shown in FIG. 19 . As shown in FIG. 19 , the oscillations in the reflectance spectrum are small (i.e., less than about 1 percentage point over the optical wavelength regime), which would lead to a relatively low visible color shift when viewed at an incidence viewing angle in the range from about 0 degrees to about 60 degrees to normal incidence, under an illuminant.

Example 6

Modeled Example 6 included an article 600 with a chemically strengthened alkali aluminoborosilicate substrate 610 and an optical film 620 disposed on the substrate. The optical film 620 included an optical interference layer 630, a scratch resistant layer 640 disposed on the optical interference layer, and a capping layer 650 disposed on the scratch-resistant layer 650. The optical interference layer included two sets of sub-layers 631A, 631B and a third sub-layer 631C disposed between the plurality of sub-layers and the substrate, as shown in FIG. 20 . The optical film materials and thicknesses of each layer, in the order arranged in the optical film, are provided in Table 13.

TABLE 13 Optical film attributes for modeled Example 6. Layer Material Modeled Thickness Ambient medium Air Immersed Capping layer RS-SiO₂   10 nm Scratch-resistant layer Si_(u)Al_(v)O_(x)N_(y)  2000 nm Optical 2^(nd) high RI sub-layer E-Ta₂O₅ 15.27 nm interference 1^(st) low RI sub-layer E-SiO₂ 19.35 nm layer 2^(nd) high RI sub-layer E-Ta₂O₅ 32.53 nm 1^(st) low RI sub-layer E-SiO2 43.18 nm Third sub-layer E-Ta₂O₅ 12.64 nm Substrate ABS Glass Immersed

The calculated reflectance spectrum for the modeled Example 6 is shown in FIG. 21 . As shown in FIG. 21 , the oscillations in the reflectance spectrum are small (i.e., less than about 1 percentage point over the optical wavelength regime), leading to relatively low calculated visible color shift for a 10 degree observer, over a range of incidence viewing angles from 60 degrees to normal incidence, under an F2 illuminant, as shown in FIG. 26 . FIG. 26 shows a target having a radius of 0.2, centered on the color coordinates of the substrate without the optical film disposed thereon, under F2 illumination.

Example 7

Modeled Example 7 included an article 700 with a chemically strengthened alkali aluminoborosilicate substrate 710 and an optical film 720 disposed on the substrate. The optical film 720 included an optical interference layer 730, a scratch resistant layer 740 disposed on the optical interference layer, and a capping layer 750 disposed on the scratch-resistant layer 750. The optical interference layer included three sets of sub-layers 731A, 731B, and a third sub-layer 731C between the plurality of sub-layers and the substrate, as shown in FIG. 22 . The optical film materials and thicknesses of each layer, in the order arranged in the optical film, are provided in Table 14.

TABLE 14 Optical film attributes for modeled Example 7. Layer Material Modeled Thickness Ambient medium Air Immersed Capping layer RS-SiO₂   10 nm Scratch-resistant layer Si_(u)Al_(v)O_(x)N_(y)  2000 nm Optical 2^(nd) high RI sub-layer E-Ta₂O₅ 18.67 nm interference 1^(st) low RI sub-layer E-SiO₂  13.7 nm layer 2^(nd) high RI sub-layer E-Ta₂O₅ 39.23 nm 1^(st) low RI sub-layer E-SiO₂ 32.77 nm 2^(nd) high RI sub-layer E-Ta₂O₅ 24.91 nm 1^(st) low RI sub-layer E-SiO₂ 50.89 nm Third sub-layer E-Ta₂O₅  8.39 nm Substrate ABS Glass Immersed

The calculated reflectance spectrum for the modeled Example 7 is shown in FIG. 22 . As shown in FIG. 22 , the oscillations in the reflectance spectrum are small (i.e., less than about 0.5 percentage points over the optical wavelength regime and, in some cases, less than about 0.1 percentage points over the optical wavelength regime), leading to relatively low calculated visible color shift for a 10 degree observer, over a range of incidence viewing angles from 60 degrees to normal incidence, under an F2 illuminant, as shown in FIG. 26 .

Example 8

Modeled Example 8 included an article 800 with a chemically strengthened alkali aluminoborosilicate substrate 810 and an optical film 820 disposed on the substrate. The optical film 820 included an optical interference layer 830, a scratch resistant layer 840 disposed on the optical interference layer, and a capping layer 850 disposed on the scratch-resistant layer 840. The optical interference layer included four sets of sub-layers 831A, 831B, and a third sub-layer 831C disposed between the plurality of sub-layers and the scratch-resistant layer, as shown in FIG. 23 . The optical film materials and thicknesses of each layer, in the order arranged in the optical film, are provided in Table 15.

TABLE 15 Optical film attributes for modeled Example 8. Layer Material Modeled Thickness Ambient medium Air Immersed Capping layer RS-SiO₂   10 nm Scratch-resistant layer Si_(u)Al_(v)O_(x)N_(y)  2000 nm Optical Third sub-layer E-Ta₂O₅ 19.52 nm interference 1^(st) low RI sub-layer E-SiO₂ 11.28 nm layer 2^(nd) high RI sub-layer E-Ta₂O₅ 44.68 nm 1^(st) low RI sub-layer E-SiO₂ 25.72 nm 2^(nd) high RI sub-layer E-Ta₂O₅ 34.69 nm 1^(st) low RI sub-layer E-SiO₂ 45.76 nm 2^(nd) high RI sub-layer E-Ta₂O₅ 20.24 nm 1^(st) low RI sub-layer E-SiO₂ 57.29 nm 2^(nd) high sub-layer E-Ta₂O₅  6.64 nm Substrate ABS Glass Immersed

The calculated reflectance spectrum for the modeled Example 8 is shown in FIG. 25 . As shown in FIG. 25 , the oscillations in the reflectance spectrum are small (i.e., less than about 0.25 percentage points over the optical wavelength regime and, in some cases, less than about 0.1 percentage points over the optical wavelength regime), leading to relatively low calculated visible color shift for a 10 degree observer, over a range of incidence viewing angles from 60 degrees to normal incidence, under an F2 illuminant, as shown in FIG. 26 .

Example 9

Modeled Example 9 included an article 900 with a chemically strengthened alkali aluminoborosilicate substrate 910 and an optical film 920 disposed on the substrate. The optical film 920 included an optical interference layer 930, a scratch resistant layer 940 disposed on the optical interference layer, and a capping layer 950 disposed on the scratch-resistant layer 950. The optical interference layer included three sets of sub-layers 931A, 931B, and a third sub-layer 931C between the plurality of sub-layers and the scratch-resistant layer, as shown in FIG. 27 . The optical film materials and thicknesses of each layer, in the order arranged in the optical film, are provided in Table 16.

TABLE 16 Optical film attributes for modeled Example 9. Layer Material Modeled Thickness Ambient medium Air Immersed Capping layer RS-SiO₂   14 nm Scratch-resistant layer Si_(u)Al_(v)O_(x)N_(y)  2000 nm Optical Third sub-layer RS-Nb₂O₅  7.0 nm interference 1^(st) low RI sub-layer RS-SiO₂ 23.02 nm layer 2^(nd) high RI sub-layer RS-Nb₂O₅ 19.75 nm 1^(st) low RI sub-layer RS-SiO₂ 41.60 nm 2^(nd) high RI sub-layer RS-Nb₂O₅ 14.68 nm 1^(st) low RI sub-layer RS-SiO₂ 57.14 nm 2^(nd) high sub-layer RS-Nb₂O₅  5.08 nm Substrate ABS Glass Immersed

The calculated reflectance spectrum for the modeled Example 9 is shown in FIG. 28 . As shown in FIG. 28 , the oscillations in the reflectance spectrum are small (i.e., less than about 1 percentage points over the optical wavelength regime and, in some cases, less than about 0.1 percentage points over the optical wavelength regime), which would lead to a relatively low visible color shift at an incidence viewing angle in the range from about 0 degrees to about 60 degrees to normal incidence, under an illuminant.

Examples 10-11 and Comparative Example 12

Example 10 was made and included a substrate, and an optical film disposed on the substrate. The substrate included a chemically strengthened ABS glass substrate having a compressive stress of about 900 MPa and a DOL of about 45 μm. As shown in Table 17, the optical film included an optical interference layer with six sub-layer sets. The six sub-layer sets included first low RI sub-layer of SiOxNy (having a refractive index value of about 1.49 at a wavelength of about 550 nm) and a second high RI sub-layer of AlO_(x)N_(y) (having a refractive index value of about 2.0 at a wavelength of about 550 nm). The optical film also included an AlO_(x)N_(y) scratch resistant layer. The optical interference layer of Example 10 was formed using reactive magnetron sputtering using an AJA-Industries sputter deposition tool using oxidizing and nitridizing environments. Sputter targets used included a 3″ diameter silicon target and a 3″ diameter aluminum target.

The first low RI layer was formed by supplying about 490 W RF to the silicon target. During formation of the first low RI layer, about 75 W RF and 50 W DC were supplied to the aluminum target; however, the aluminum shutter was closed to prevent deposition of aluminum. During deposition of the first low RI sub-layers, oxygen was flowed into the reactor at a flow rate of about 3.3 sccm, argon was flowed into the reactor at a flow rate of about 30 sccm and nitrogen gas was flowed into the reactor at a flow rate of about 30 sccm. The deposition times for the first low RI sub-layers were modified to provide the thicknesses shown in Tables 17 and 18.

The second high RI sub-layers were disposed using RF superimposed DC power directed at the aluminum target. About 300 W of DC power was supplied to the aluminum target and about 200 W of RF power was supplied to the Al target. During formation of the second high RI layer, RF power was supplied to the silicon target at about 50 W; however, the silicon shutter was closed to prevent deposition of silicon. During deposition of the second high RI sub-layers, oxygen was flowed into the reactor at a flow rate of 0.25 sccm, argon was flowed into the reactor at a flow rate of about 30 sccm and nitrogen gas was flowed into the rector at a rate of about 30 sccm. The deposition times for the second high RI sub-layers were modified to provide the thicknesses shown in Tables 17 and 18.

Table 17 also provides the refractive index values for the respective first low RI sub-layers, second high RI sub-layers and the scratch-resistant layer, at a wavelength of about 550 nm. The entire dispersion curves for these sub-layers are similar to analogous materials used in Modeled Examples 1-9 (whose refractive index dispersions were also measured experimentally). Dispersion curves used in Modeled Examples 1-9 can be shifted up or down slightly by a linear or scaled amount at each wavelength to arrive at the target refractive indices used in Examples 10 and 11 to very closely reproduce the actual dispersion curves of the materials in working Examples 10 and 11.

At each of the transitions between the first low RI sub-layers (SiOxNy) and the second high RI sub-layers (AlOxNy), both the silicon and aluminum shutters were closed for about 60 seconds, as the gas flows were transitioned to those required for the following sub-layer. During this transition, the powers and gas flows were adjusted. The sputtering was maintained “on” but the sputtered material went onto the closed shutter. The power supplied to the silicon target was left at about 500 W in some cases to scavenge remnant oxygen, since the second high RI sub-layer utilized a low oxygen flow (as compared to the oxygen flow used to form the first low RI sub-layer). This process allowed the sputter targets to attain their desired powers, in the presence of the gases that were used for the various layers, prior to opening the shutters for a given sub-layer.

The scratch-resistant layer was formed using the same conditions as used to form the second high RI sub-layers. The resulting scratch-resistant layer combined with the optical interference layers as described exhibited a hardness of about 15 GPa, as measured using a Berkovich indenter as described herein and a modulus of about 212 GPa as measured by known nanoindentation methods.

TABLE 17 Optical film target refractive indices and thicknesses for Example 10. Target Refractive Target Layer Material Index @550 nm Thickness (nm) Scratch-resistant layer AlO_(x)N_(y) 2.00709 2000 First low RI sub-layer SiO_(x)N_(y) 1.49658 9.7 Second high RI sub- AlO_(x)N_(y) 2.00709 42.17 layer First low RI sub-layer SiO_(x)N_(y) 1.49658 30.27 Second high RI sub- AlO_(x)N_(y) 2.00709 24.68 layer First low RI sub-layer SiO_(x)N_(y) 1.49658 52.71 Second high RI sub- AlO_(x)N_(y) 2.00709 8.25 layer Substrate ABS glass 1.51005

TABLE 18 Sputtering process conditions used for Example 10. Sputter Time Si W Si Al W Al W Al O₂ Ar N₂ Layer Material (sec) RF shutter RF DC shutter flow flow flow Scratch-resistant AlO_(x)N_(y) 32756.6 50 closed 200 300 open 3.3 30 30 layer First low RI SiO_(x)N_(y) 121.9 490 open 75 50 closed 0.25 30 30 sub-layer Second high RI AlO_(x)N_(y) 710.3 50 closed 200 300 open 3.3 30 30 sub-layer First low RI SiO_(x)N_(y) 448.3 490 open 75 50 closed 0.25 30 30 sub-layer Second high RI AlO_(x)N_(y) 440.6 50 closed 200 300 open 3.3 30 30 sub-layer First low RI SiO_(x)N_(y) 804.2 490 open 75 50 closed 0.25 30 30 sub-layer Second high RI AlO_(x)N_(y) 104.3 50 closed 200 300 open 3.3 30 30 sub-layer Substrate ABS glass Total Time: 35523.0

Example 11 was formed using the same equipment and similar reactive sputtering processes as Example 10; however Example 11 included Si_(u)Al_(v)O_(x)N_(y) in the second high RI sub-layers and as the scratch resistant layer, which had a refractive index at a wavelength of about 550 nm of about 1.998. The same substrate was used in Example 11 as was used in Example 10. The optical film design for Example 11 and sputtering process conditions used to form Example 11 are shown in Tables 19 and 20.

Example 11 was measured for hardness using a Berkovich diamond indenter and an indentation depth of about 100 nm, as described herein, and the article of Exhibit 11 had a measured hardness of 21 GPa. Example 11 also exhibited an elastic modulus of 237 GPa.

TABLE 19 Optical film target refractive indices and thicknesses for Example 11. Target Refractive Target Layer Material Index @550 nm Thickness (nm) Scratch-resistant Si_(u)Al_(v)O_(x)N_(y) 1.99823 2000 layer First low RI sub- SiO_(x)N_(y) 1.49594 11.8 layer 1. Second high RI Si_(u)Al_(v)O_(x)N_(y) 1.99823 45.4 sub-layer First low RI sub- SiO_(x)N_(y) 1.49594 33.6 layer Second high RI Si_(u)Al_(v)O_(x)N_(y) 1.99823 27.5 sub-layer First low RI sub- SiO_(x)N_(y) 1.49594 56.5 layer Second high RI Si_(u)Al_(v)O_(x)N_(y) 1.99823 10.1 sub-layer Substrate ABS glass 1.51005

TABLE 20 Sputtering process conditions for Example 11. Sputter Time Si W Si Al W Al W Al O2 Ar N2 Layer Material (sec) RF shutter RF DC shutter flow flow flow Scratch-resistant Si_(u)Al_(v)O_(x)N_(y) 18340.0 500 open 200 300 open 3.3 30 30 layer First low RI SiO_(x)N_(y) 135.0 500 open 50 50 closed 0.5 30 30 sub-layer Second high RI Si_(u)Al_(v)O_(x)N_(y) 440.0 500 open 200 300 open 3.3 30 30 sub-layer First low RI SiO_(x)N_(y) 385.0 500 open 50 50 closed 0.5 30 30 sub-layer Second high RI Si_(u)Al_(v)O_(x)N_(y) 275.0 500 open 200 300 open 3.3 30 30 sub-layer First low RI SiO_(x)N_(y) 640.0 500 open 50 50 closed 0.5 30 30 sub-layer Second high RI Si_(u)Al_(v)O_(x)N_(y) 195.0 500 open 200 300 open 3.3 30 30 sub-layer Substrate ABS glass Total time: 20410.0

Comparative Example 12 was formed using the same substrate as Examples 10 and 11, but film disposed on the substrate was formed by reactive sputtering using a Shincron rotary drum coater. The film of Comparative Example 12 included a single optical interference layer disposed between a scratch-resistant layer and the glass substrate. Comparative Example 12 included the following structure: glass substrate/115 nm optical interference layer of Al₂O₃/2000 nm scratch-resistant layer of AlO_(x)N_(y)/32 nm capping layer of SiO₂.

The optical properties of Examples 10 and 11 and Comparative Example 12 are summarized in FIGS. 29-31 . FIG. 29 shows the transmittance spectra for Examples 10-11 and Comparative Example 12. FIG. 30 shows the measured reflected light color coordinates for Examples 10-11 with F2 illumination at different incident illumination angles (e.g., 5, 20, 40, and 60 degrees). FIG. 31 shows the measured transmitted light color coordinates for Examples 10-11 with D65 illumination at an incident illumination angle of 5 degrees. Circular target lines are shown in FIGS. 30 and 31 as guides for the eye.

The oscillation amplitudes in transmittance for Example 10 was measured as less than about 3 percentage points for any 50 nm or 100 nm wavelength range segment, within the broader wavelength range from about 450 nm to about 650 nm, or from about 400 nm to about 700 nm. As shown in FIG. 30 , the maximum variation in reflected color coordinates for Example 10 under F2 illumination with measurement incident illumination angle varying from 5 to 60 degrees was less than +/−1.5 in b* color coordinate and less than +/−0.5 in a* color coordinate. As shown in FIG. 31 , the transmitted color coordinates for Example 10 under D65 illumination at 5 degree incident illumination angle varies from the uncoated glass color coordinates by less than +/−0.2 in b* color coordinate and less than +/−0.1 in a* color coordinate.

The oscillation amplitudes in transmittance for Example 11 was measured as less than about 3 percentage points for any 50 nm or 100 nm wavelength range segment, within the broader wavelength range from about 450 nm to about 650 nm, or from about 400 nm to about 700 nm. In some instances, the oscillation amplitude was even less than 2 percentage points from some 50 nm or 100 nm wavelength range segments. As shown in FIG. 30 , the maximum variation in reflected color coordinates for Example 11 under F2 illumination with measurement incident illumination angle varying from 5 to 60 degrees is less than +/−0.4 in both a* and b* color coordinates. As shown in FIG. 31 , the transmitted color coordinates for Example 11 under D65 illumination at 5 degrees varies from the uncoated glass color coordinates by less than +/−0.4 in b* color coordinate and less than +/−0.1 in a* color coordinate.

The oscillation amplitudes in transmittance for Comparative Example 12 were comparatively large, as shown in FIG. 29 . From this data, it can be predicted that the color coordinates a* and b* would vary substantially under the same illuminants and the same incident illumination angles as used to evaluate Examples 10 and 11.

The absolute color coordinates for Examples 10 and 11 could be further tuned by adding a capping layer (e.g., a capping layer having a thickness in the range from about 5 nm to about 25 nm of SiO₂ or SiO_(x)N_(y)), as shown in the modeled Examples. The range of color variation and reflectance/transmittance oscillations seen in Examples 10 and 11 is in a low and useful range, although the color variation is somewhat larger than that seen in the modeled Examples. This difference between the modeled Examples 1-9 and Examples 10-11 is believed to be a function of layer thickness and index variations encountered during the reactive RF sputtering process. There are a variety of methods known in the art for forming the optical films of Examples 10-11 and described herein, which were not used in these experiments, which could further improve the control of the experimentally fabricated layer and sub-layer thicknesses and refractive indices. Exemplary methods include slower deposition rates for the thinnest layers in the optical film, optical or quartz crystal thickness monitoring of layer or sub-layer thickness during deposition, plasma emission or mass spectrometric monitoring of the gas composition in the chamber during deposition; and other known techniques used to control layer thickness and composition in thin film deposition.

The optical interference layers used in the Examples were designed to minimize reflection between the scratch-resistant layer and the substrate, thus reducing reflectance oscillation for the entire article. The reduced reflectance oscillation (or reflectance oscillations having reduced amplitudes), provided low observed color and low color shifts at different incidence viewing angles under multiple illumination sources, including illumination sources with sharp wavelength spikes such as CIE F2 and F10 illumination. The scratch-resistant layer exhibited a hardness of greater than about 15 GPa when measured using a Berkovich indenter, as described herein, and in some cases even greater than 20 GPa.

Example 13

Modeled Example 13 included an article 1000 with a chemically strengthened glass substrate 1010 and an optical film 1020 disposed on the substrate. The optical film 1020 included an optical interference layer 1030, a scratch resistant layer 1040 disposed on the optical interference layer, and a capping layer 1050 disposed on the scratch-resistant layer 1040. The optical interference layer included three sets of sub-layers 1031A, 1031B, between the substrate and the scratch-resistant layer, as shown in FIG. 32 . The optical film materials and thicknesses of each layer, in the order arranged in the optical film, are provided in Table 21.

TABLE 21 Optical film attributes for modeled Example 13. Layer T Material Modeled Thickness Ambient medium Air Immersed Capping layer SiO₂  10 nm Scratch-resistant layer AlOxNy 2000 nm Optical 1^(st) low RI sub-layer SiO₂  10 nm interference 2^(nd) high RI sub-layer AlOxNy  50 nm layer 1^(st) low RI sub-layer SiO₂  25 nm 2^(nd) high RI sub-layer AlOxNy  25 nm 1^(st) low RI sub-layer SiO₂  50 nm 2^(nd) high sub-layer AlOxNy  10 nm Substrate ABS Glass Immersed

Example 13 has symmetrical optical interference layer. In one or more embodiments, the optical interference layer may be modified to have different sub-layers and sub-layers with different thicknesses so long as the symmetry is preserved.

Example 14

Example 14A was formed using an aluminosilicate glass substrate that was chemically strengthened and exhibited a compressive stress in the range from about 700 MPa to about 900 MPa and a depth of compressive stress layer in the range from about 40 about 40 μm to about 50 μm. Example 14A included an optical film including the following structure shown in Table 22, with the thickness of each layer varying by no more than 5 nm, due to manufacturing tolerances.

TABLE 22 Optical Film Attributes of Example 14A. Layer Material Thickness Capping layer SiO₂  10 nm Scratch-resistant layer AlOxNy 2000 nm Optical 1^(st) low RI sub-layer SiO₂  10 nm interference 2^(nd) high RI sub-layer AlOxNy  50 nm layer 1^(st) low RI sub-layer SiO₂  30 nm 2^(nd) high RI sub-layer AlOxNy  30 nm 1^(st) low RI sub-layer SiO₂  50 nm 2^(nd) high sub-layer AlOxNy  10 nm

Comparative Example 14B included the same substrate as Example 14A but was uncoated. Comparative Example 14C included the same substrate as Example 14A with a hydrophobic, low-friction fluorosilane coating having a thickness of about 10 nm disposed on the substrate. Comparative Examples 14D-14F included the same substrate as Example 14A with a single layer of either Si_(u)Al_(v)O_(x)N_(y) having a thickness of 186 nm (14D) or 478 nm (14E) or AlO_(x)N_(y) with a thickness of about 294 nm (14F).

The coatings on Example 14A, and Comparative Examples 14D-14F were formed using reactive DC sputtering or combined reactive DC and RF sputtering from metallic targets. It should be noted that layers of AlO_(x)N_(y) can often be substituted for the layers of Si_(u)Al_(v)O_(x)N_(y) layers and can be formed using the same or a similar process used to form such layers. Both Si_(u)Al_(v)O_(x)N_(y), and AlO_(x)N_(y) layers can be made which exhibited a refractive index at 550 nm of about 1.95-2.05 and a measured hardness greater than 15 GPa measured using the Berkovich Indentation Hardness Test along an indentation depth of about 100 nm or greater.

Table 23 shows scattered light intensity (CCBTDF, 1/steradian) and transmission haze (with 8 mm aperture) after subjecting the samples to the Taber Test. Table 23 also shows the average scattered light intensity value and haze value of Example 14A, and Comparative Examples 14B-F, as a baseline. Lower scattered light intensity and lower haze correlates to less visible scratches and less visible damage after the abrasion test. Example 14A exhibited the lowest scattered light intensity and haze after the Taber Test indicating superior resistance to multiple contact event damage.

TABLE 23 Scattered Light Intensity and Haze Measurements for Example 14A and Comparative Examples 14B-14F. Scattered light intensity − Avg. +/− Std. Dev. Range of (CCBTDF, Transmission 1/steradian) Haze Examples At 20 degrees With 8 mm aperture Comparative Example 14B − 0.021 +/− 0.004 0.1-0.4 IX glass (no coating) Comparative Example 14C − 0.022 +/− 0.015 0.25-0.35 IX Glass + hydrophobic, low-friction fluorosilane coating Comp. Ex. 14D − IX Glass + 1L  0.03 +/− 0.01 0.8 SiuAlvOxNy 186 nm Comp. Ex. 14E − IX Glass + 1L 0.018 +/− 0.001 0.3 SiuAlvOxNy 478 nm Comp. Ex. 14F − IX Glass + 1L 0.174 +/− 0.04 5.1 AlOxNy 294 nm Example 14A 3L SRC Al₂O₃/ 0.002 +/− 0.0001 0.05 AlON/SiO₂ Average of non-abraded 0.002 +/− 0.001   0-0.2 regions of Examples 14A and Comparative Examples 14B-12F

Example 14A was also subjected to the Garnet Test (separately from the Taber Test) at different total loads, as shown in Table 24. Comparative Example 14B was also subjected to the Garnet Test (separately from the Taber Test) for comparison.

TABLE 24 Garnet Test results of Example 14A and Comparative Example 14B. Scattered light at Haze (with 8 mm aperture) after Garnet 20 degrees Test with specified total load (g) (CCBTDF, 1/sr) Total Load applied 380 g 500 g 750 g 1500 g 2100 g 2100 g Comparative Ex. 14B 0.4 0.5 1.2 3.2 3.5 0.053 +/− 0.03  Example 14A 0 0 0 0 0.1  0.002 +/− 0.0005

As shown in Table 24, Example 14A exhibited significantly less haze and less scattered light after the Garnet Test at all loads as compared to Comparative Example 14B.

It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit or scope of the invention. 

What is claimed is:
 1. A cover article comprising: a substrate having a surface, and an optical film disposed on the substrate surface forming a coated surface, the optical film comprising a scratch-resistant layer and an optical interference layer; wherein the optical interference layer comprises a first low refractive index (RI) sub-layer and a second high refractive index (RI) sub-layer, wherein the difference between the refractive index of the first low RI sub-layer and the refractive index of the second high RI sub-layer is 0.01 or greater; and, wherein the cover article comprises an average hardness of 8 GPa or greater, as measured by a Berkovich Indenter Hardness Test along indentation depths of 100 nm or greater.
 2. The cover article of claim 1, wherein the scratch-resistant layer comprises one or more of AlN, Si₃N₄, AlO_(x)N_(y), SiO_(x)N_(y), Al₂O₃, Si_(x)C_(y), Si_(x)O_(y)C_(z), ZrO₂, TiO_(x)N_(y), diamond, diamond-like carbon, silicon nitride, silicon oxynitride, and Si_(u)Al_(v)O_(x)N_(y).
 3. The cover article of claim 1, wherein the scratch-resistant layer has a physical thickness of from 0.1 micrometres to 3 micrometres.
 4. The cover article of claim 1, wherein the cover article comprises a color shift of 2 or less, when viewed at at least one incident illumination angle in the range from 5 degrees to 60 degrees from normal incidence under an illuminant comprising CIE A illuminants, CIE B illuminants CIE C illuminants, CIE D illuminants or CIE F illuminants, and further wherein color shift is determined by the equation √((a*₂−a*₁)²+(b*₂−b*₁)²), where a*₁ and b*₁ are coordinates of the article when viewed at normal incidence and a*₂, and b*₂ are coordinates of the article viewed at the at least one incident illumination angle, and wherein the coordinates of the article when viewed at normal incidence and at the at least one incident illumination angle are both in transmittance or reflectance.
 5. The cover article of claim 1, wherein the first low RI sub-layer comprises a contiguous and uninterrupted sub-layer of SiO₂ that is disposed in direct contact with the substrate surface.
 6. The cover article of claim 1, wherein the first low RI sub-layer has a refractive index from about 1.4 to about 1.5, as measured from about 380 nm to about 750 nm.
 7. The cover article of claim 1, wherein the optical interference layer comprises a physical thickness of (1) from about 50 nm to about 300 nm, (2) from about 50 nm to about 450 nm, (3) from 50 nm to about 500 nm or (4) from 50 nm to about 800 nm.
 8. The cover article of claim 1, wherein the second high RI sub-layer comprises an optical thickness (n*d) in the range from about 2 nm to about 200 nm where n is the refractive index and d is the physical thickness of the second high RI sub-layer.
 9. The cover article of claim 1, wherein the substrate comprises a glass selected from the group consisting of soda lime glass, alkali aluminosilicate glass, alkali containing borosilicate glass and alkali aluminoborosilicate glass.
 10. The cover article of claim 1, wherein the substrate comprises a crystalline substrate, or a glass ceramic substrate.
 11. The cover article of claim 1, wherein: the first low RI sub-layer comprises silicon-containing oxide disposed on the substrate surface, and a physical thickness from 12 nm to about 135 nm; the second RI sub-layer comprises a silicon-containing nitride or a silicon-containing oxynitride; and, the scratch resistant layer comprises a silicon-containing nitride, a silicon-containing oxynitride or Si_(u)Al_(v)O_(x)N_(y), and a physical thickness of from 0.1 micrometres to 3 micrometres.
 12. The cover article of claim 11, wherein: the silicon-containing oxide comprises SiO₂ or SiO, the silicon-containing nitride comprises Si₃N₄, and the silicon-containing oxynitride comprises Si_(u)Al_(v)O_(x)N_(y) or SiO_(x)N_(y).
 13. The cover article of claim 1, wherein the cover article is part of a smart phone, a mobile phone, a tablet, a computer, or a navigation system.
 14. The cover article of claim 1, wherein the optical interference layer further comprises a third sub-layer which has (1) a same RI as the first low RI sub-layer; (2) a same RI as the second high RI sub-layer, or (3) a medium RI that is between the RI of the first low RI sub-layer and the RI of the second high RI sub-layer.
 15. The cover article of claim 1, further comprises: a capping layer disposed on the scratch-resistant layer, the capping layer comprises a contiguous and uninterrupted sub-layer of SiO₂, and a physical thickness of from 0 to 100 nm.
 16. The cover article of claim 1, further comprises: a capping layer disposed on the scratch-resistant layer, the capping layer comprises two or more materials or two or more sub-layers.
 17. The cover article of claim 16, wherein the two or more sub-layers of the capping layer have different refractive indices and include layers with high refractive indices (H) and low refractive indices (L) where the high refractive indices (H) and the low refractive indices (L) are with respect to one another.
 18. The cover article of claim 17, wherein the two or more sub-layers of the capping layer are arranged so that high and low refractive index sub-layers alternate.
 19. The cover article of claim 18, wherein the two or more sub-layers of the capping layer have a thickness each or combined in the range from about 4 nm to about 50 nm.
 20. The cover article of claim 16, wherein the capping layer includes a silane-based low-friction sub-layer having a thickness in the range from about 0.1 nm to about 20 nm, disposed on underlying sub-layers of the capping layer.
 21. The cover article of claim 1, wherein the cover article further comprises a crack mitigating layer.
 22. The device of claim 1, wherein the cover article further comprises a color shift of 2 or less, when viewed at each of the incident illumination angles in the range from about 5 degrees to about 45 degrees from normal incidence under an illuminant comprising CIE A illuminants, CIE B illuminants, CIE C illuminants, CIE D illuminants or CIE F illuminants, and further wherein color shift is determined by the equation √((a*₂−a*₁)²+(b*₂−b*₁)²), where a*₁ and b*₁ are coordinates of the article when viewed at normal incidence and a*₂ and b*₂ are coordinates of the article viewed at each of the incident illumination angles, and wherein the coordinates of the article when viewed at normal incidence and at each of the incident illumination angles are both in transmittance or reflectance.
 23. The cover article of claim 1, wherein the cover article further comprises a color shift of 2 or less, when viewed at each of the incident illumination angles in the range from about 5 degrees to about 60 degrees from normal incidence under an illuminant comprising CIE A illuminants, CIE B illuminants, CIE C illuminants, CIE D illuminants or CIE F illuminants, and further wherein color shift is determined by the equation √((a*₂−a*₁)²+(b*₂−b*₁)²), where a*₁ and b*₁ are coordinates of the article when viewed at normal incidence and a*₂ and b*₂ are coordinates of the article viewed at each of the incident illumination angles, and wherein the coordinates of the article when viewed at normal incidence and at each of the incident illumination angles are both in transmittance or reflectance.
 24. A cover article comprising: a substrate having a surface, and an optical film disposed on the substrate surface forming a coated surface, the optical film having a physical thickness in a range from about 0.1 μm to about 3 μm; wherein the optical film comprises an average hardness in a range from about 8 GPa to about 30 GPa as measured by a Berkovich Indenter Hardness Test along indentation depths of 100 nm or greater; and, wherein the cover article exhibits an average transmittance of 85% or greater over the visible spectrum.
 25. The cover article of claim 24, wherein the optical film further comprising a scratch-resistant layer and an optical interference layer, wherein the optical interference layer disposed between the scratch-resistant layer and the substrate.
 26. The cover article of claim 25, wherein the scratch-resistant layer comprises one or more of AlN, Si₃N₄, AlO_(x)N_(y), SiO_(x)N_(y), Al₂O₃, Si_(x)C_(y), Si_(x)O_(y)C_(z), ZrO₂, TiO_(x)N_(y), diamond, diamond-like carbon, silicon nitride, silicon oxynitride, and Si_(u)Al_(v)O_(x)N_(y).
 27. The cover article of claim 25, wherein the optical interference layer comprises a first low refractive index (RI) sub-layer and a second high refractive index (RI) sub-layer, wherein: the first low RI sub-layer comprises at least one of SiO₂, Al₂O₃, GeO₂, SiO, AlO_(x)N_(y), SiO_(x)N_(y), Si_(u)Al_(v)O_(x)N_(y), MgO, MgF₂, BaF₂, CaF₂, DyF₃, YbF₃, YF₃, and CeF₃; and the second high RI sub-layer comprises at least one of Si_(u)Al_(v)O_(x)N_(y), Ta₂O₅, Nb₂O₅, AlN, Si₃N₄, AlO_(x)N_(y), SiO_(x)N_(y), HfO₂, TiO₂, ZrO₂, Y₂O₃, Al₂O₃, and MoO₃.
 28. The cover article of claim 24, wherein the cover article further comprises a color shift of 2 or less, when viewed at at least one incident illumination angle in the range from about 5 degrees to about 60 degrees from normal incidence under an illuminant comprising CIE A illuminants, CIE B illuminants, CIE C illuminants, CIE D illuminants or CIE F illuminants, and further wherein color shift is determined by the equation √((a*₂−a*₁)²+(b*₂−b*₁)²), where a*₁ and b*₁ are coordinates of the article when viewed at normal incidence and a*₂ and b*₂ are coordinates of the article viewed at the at least one incident illumination angle, and wherein the coordinates of the article when viewed at normal incidence and at the at least one incident illumination angle are both in transmittance or reflectance.
 29. The cover article of claim 24, wherein the substrate comprises a crystalline substrate, or a glass ceramic substrate.
 30. The cover article of claim 24, wherein the cover article is part of a smart phone, a mobile phone, a tablet, a computer, or a navigation system.
 31. A cover article comprising: a substrate having a surface; an optical film disposed on the substrate surface forming a coated surface, the optical film comprising a scratch-resistant layer and an optical interference layer disposed between the scratch-resistant layer and the substrate; wherein the optical interference layer comprises a first low refractive index (RI) sub-layer and a second high refractive index (RI) sub-layer; wherein the first low RI sub-layer comprises silicon-containing oxide disposed on the substrate surface; wherein the second high RI sub-layer comprises a silicon-containing nitride or a silicon-containing oxynitride; and, wherein the scratch resistant layer comprises a silicon-containing nitride, a silicon-containing oxynitride or Si_(u)Al_(v)O_(x)N_(y). 